Skin care compositions and method of improving skin appearance

ABSTRACT

Disclosed are topical compositions which provide good coverage of skin imperfections, e.g., pores and uneven skin tone, while retaining a natural skin appearance. The compositions contain a particulate material having a refractive index of at least about 2, e.g., TiO 2 .

This is a CIP of application Ser. No. 08/862,775 filed May 23, 1997 nowabandoned.

TECHNICAL FIELD

The present invention relates to the field of topical compositions forimproving the appearance or other condition of skin. More particularly,the invention relates to topical compositions which provide goodcoverage of skin imperfections, e.g., pores and uneven skin tone, whileretaining a natural skin appearance.

BACKGROUND

A variety of compounds have been described in the art as being usefulfor regulating fine lines, wrinkles and other forms of undesirable skinsurface texture. In addition, Vitamin B₃ compounds, particularlyniacinamide, have recently been found to provide measurable benefits inregulating skin condition, including regulating fine lines, wrinkles andother forms of uneven or rough surface texture associated with aged orphotodamaged skin. However, many materials require multiple applicationsover an extended period to provide such appearance benefits. It would beadvantageous to provide a topical composition which provides a moreimmediate improvement in the appearance of fine lines, wrinkles, poresand other forms of undesirable skin surface texture.

Particulate materials, including TiO₂, have been included in skin carecompositions. For example, emulsions may contain TiO₂ as an opacifyingagent to provide a white appearance to the emulsion. Commercialsunscreening compositions may employ such particulates to impart asunscreening effect. Several publications have also disclosed the use ofTiO₂ in skin care compositions. See, e.g., U.S. Pat. No. 5,223,559 andpatent application Nos. DE 245815, WO 94/09756 and JP 08188723. Inaddition, R. Emmert has stated the desire to use optical means toformulate products that give the consumer an immediate, visualimprovement (Dr. Ralf Emmert, Quantification of the Soft-Focus Effect,Cosmetics & Toiletries, Vol. 111, July 1996, pp. 57-61). Emmertdiscloses that one can mechanically fill in skin lines with a reflectivesubstance such as TiO₂. However, Emmert teaches that such reflectivematerials result in an undesirable mask-like appearance, and that oneshould therefore use a material that diffuses light yet is sufficientlytransparent to avoid the mask-like appearance.

Previous topical compositions containing reflective materials such asTiO₂, of which the present inventors are aware, either do not providecoverage sufficient to reduce the appearance of skin imperfections, ortend to result in unacceptable skin whitening or other unnaturalappearance when applied to the skin. It has also now been found thatmaterials which primarily diffuse light, rather than reflect light, donot provide good coverage of skin imperfections when used in amountswhich are esthetically acceptable to consumers. More particularly, whenused at relatively high concentrations to provide coverage, thesematerials suffer from unacceptable skin whitening.

The present inventors have now found that reflective materials such asTiO₂ can be formulated in topical compositions to provide good coverageof skin imperfections while retaining a generally natural appearance,e.g., without unacceptable skin whitening. The compositions areespecially suitable for providing an immediate visual improvement inskin appearance.

It is an object of the present invention to provide topical compositionssuitable for imparting an essentially immediate visual improvement inskin appearance. It is another object of the present invention toprovide topical compositions containing a reflective particulatematerial, e.g., TiO₂, which provide desirable coverage of skinimperfections such as pores and uneven skin tone, while maintaining anatural skin appearance (e.g., without unacceptable skin whitening).Another object of the present invention is to provide such topicalcompositions which are additionally useful for regulating skinappearance and/or condition, especially regulating textural or tonaldiscontinuities in skin (e.g., pores and uneven skin color).

The present invention also relates to methods of improving skinappearance and/or condition by topical application of the subjectcompositions.

These and other objects of this invention will become apparent in lightof the following disclosure.

SUMMARY OF THE INVENTION

The present invention relates to topical compositions comprising aparticulate material and a topical carrier, the particulate materialhaving a refractive index of at least about 2 and a neat primaryparticle size of from about 100 nm to about 300 nm. The compositionpreferably contains from about 0.3% to about 2% of the particulatematerial. Preferred particulates are selected from TiO₂, ZnO, and ZrO,with TiO₂ being more preferred. The compositions are useful forimparting an essentially immediate visual improvement in skinappearance, while maintaining a natural skin appearance. Compositions ofthe invention are characterized by their contrast ratio and %transmittance or Coverage Index. Compositions of the invention have acontrast ratio of from about 9 to about 30 and a % transmittance of fromabout 92% to about 62%. Preferred compositions can be furthercharacterized by their apparent viscosity and Hydration Factor.

DETAILED DESCRIPTION OF THE INVENTION

All percentages and ratios used herein are by weight of the totalcomposition and all measurements made are at 25° C., unless otherwisedesignated.

The compositions of the present invention can comprise, consistessentially of, or consist of, the essential as well as optionalingredients and components described herein. As used herein, "consistingessentially of" means that the composition or component may includeadditional ingredients, but only if the additional ingredients do notmaterially alter the basic and novel characteristics of the claimedcompositions or methods.

All publications cited herein are hereby incorporated by reference intheir entirety.

The term "topical application", as used herein, means to apply or spreadthe compositions of the present invention onto the surface of the skin.

The term "dermatologically-acceptable," as used herein, means that thecompositions or components thereof so described are suitable for use incontact with human skin without undue toxicity, incompatibility,instability, allergic response, and the like.

The term "safe and effective amount" as used herein means an amount of acompound, component, or composition sufficient to significantly induce apositive benefit, preferably a positive skin appearance or feel benefit,including independently the benefits disclosed herein, but low enough toavoid serious side effects, i.e., to provide a reasonable benefit torisk ratio, within the scope of sound medical judgment.

Active and other ingredients useful herein may be categorized ordescribed herein by their cosmetic and/or therapeutic benefit or theirpostulated mode of action. However, it is to be understood that theactive and other ingredients useful herein can in some instances providemore than one cosmetic and/or therapeutic benefit or operate via morethan one mode of action. Therefore, classifications herein are made forthe sake of convenience and are not intended to limit an ingredient tothe particularly stated application or applications listed.

The compositions of the invention are useful for topical application andfor providing an essentially immediate (i.e., acute) visual improvementin skin appearance following application of the composition to the skin.Without intending to be limited by theory, it is believed that thisacute skin appearance improvement results at least in part fromtherapeutic coverage or masking of skin imperfections by the particulatematerial. The compositions provide the visual benefits without impartingan unacceptable skin appearance such as skin whitening.

More particularly, the compositions of the present invention are usefulfor regulating skin condition, including regulating visible and/ortactile discontinuities in skin, including but not limited to visibleand/or tactile discontinuities in skin texture and/or color, moreespecially discontinuities associated with skin aging. Suchdiscontinuities may be induced or caused by internal and/or externalfactors. Extrinsic factors include ultraviolet radiation (e.g., from sunexposure), environmental pollution, wind, heat, low humidity, harshsurfactants, abrasives, and the like. Intrinsic factors includechronological aging and other biochemical changes from within the skin.

Regulating skin condition includes prophylactically and/ortherapeutically regulating skin condition. As used herein,prophylactically regulating skin condition includes delaying, minimizingand/or preventing visible and/or tactile discontinuities in skin. Asused herein, therapeutically regulating skin condition includesameliorating, e.g., diminishing, minimizing and/or effacing, suchdiscontinuities. Regulating skin condition involves improving skinappearance and/or feel, e.g., providing a smoother, more even appearanceand/or feel. As used herein, regulating skin condition includesregulating signs of aging. "Regulating signs of skin aging" includesprophylactically regulating and/or therapeutically regulating one ormore of such signs (similarly, regulating a given sign of skin aging,e.g., lines, wrinkles or pores, includes prophylactically regulatingand/or therapeutically regulating that sign).

"Signs of skin aging" include, but are not limited to, all outwardvisibly and tactilely perceptible manifestations as well as any othermacro or micro effects due to skin aging. Such signs may be induced orcaused by intrinsic factors or extrinsic factors, e.g., chronologicalaging and/or environmental damage. These signs may result from processeswhich include, but are not limited to, the development of texturaldiscontinuities such as wrinkles, including both fine superficialwrinkles and coarse deep wrinkles, skin lines, crevices, bumps, largepores (e.g., associated with adnexal structures such as sweat glandducts, sebaceous glands, or hair follicles), scaliness, flakiness and/orother forms of skin unevenness or roughness, loss of skin elasticity(loss and/or inactivation of functional skin elastin), sagging(including puffiness in the eye area and jowls), loss of skin firmness,loss of skin tightness, loss of skin recoil from deformation,discoloration (including undereye circles), blotching, sallowness,hyperpigmented skin regions such as age spots and freckles, keratoses,abnormal differentiation, hyperkeratinization, elastosis, collagenbreakdown, and other histological changes in the stratum corneum,dermis, epidermis, the skin vascular system (e.g., telangiectasia orspider vessels), and underlying tissues, especially those proximate tothe skin.

It is to be understood that the present invention is not to be limitedto regulation of the above mentioned "signs of skin aging" which arisedue to mechanisms associated with skin aging, but is intended to includeregulation of said signs irrespective of the mechanism of origin. Asused herein, "regulating skin condition" is intended to includeregulation of such signs irrespective of the mechanism of origin.

The present invention is especially useful for therapeuticallyregulating visible and/or tactile discontinuities in mammalian skin,including discontinuities in skin texture and color. For example, theapparent diameter of pores decreases, the apparent height of tissueimmediately proximate to pore openings approaches that of theinteradnexal skin, the skin tone/color becomes more uniform, and/or thelength, depth, and/or other dimension of lines and/or wrinkles aredecreased.

Particulate material

The compositions of the present invention comprise a safe and effectiveamount of a particulate material having a refractive index of at leastabout 2, more preferably at least about 2.5, e.g., from about 2 to about3. The particulate material is dispersed in a dermatologicallyacceptable carrier.

Refractive index can be determined by conventional methods. For example,a method for determining the refractive index which is applicable to thepresent invention is described in J. A. Dean, Ed., Lange's Handbook ofChemistry, 14th Ed., McGraw Hill, New York, 1992, Section 9,Refractometry, incorporated herein by reference in its entirety.

The particulate material preferably comprises particles of inorganicmaterial comprising TiO₂, ZnO, ZrO₂ and combinations thereof, morepreferably TiO₂, ZnO and combinations thereof (combinations are intendedto include particles which comprise one or more of these materials, aswell as mixtures of these particulate materials). The particulatematerial may be a composite, e.g., deposited on a core or mixed withother materials such as but not limited to silica, silicone, mica, nylonand polyacrylates, provided that the material has the aforementionedrefractive index. The particulate preferably consists essentially ofTiO₂, ZnO, ZrO₂ or a combination thereof, more preferably TiO₂, ZnO or acombination thereof, most preferably, the particles consist essentiallyof TiO₂.

Pigmentary grade particulate material is preferred. Preferredparticulate materials are those having a primary particle size of fromabout 100 nm to about 300 nm, more preferably greater than 100 nm toabout 300 nm, even more preferably from about 150 nm to about 300 nm,most preferably from about 200 nm to about 250 nm (e.g., about 220 toabout 240 nm), in the neat form (i.e., in the essentially pure, powderform prior to combination with any carrier). Preferred particulatematerials have a primary particle size when dispersed in the compositionof from about 100 nm to about 1000 nm (preferably greater than 100 nm),more preferably from about 100 nm to about 400 nm, even more preferablyfrom about 200 nm to about 300 nm. Primary particle size can bedetermined using the ASTM Designation E20-85 "Standard Practice forParticle Size Analysis of Particulate Substances in the Range of 0.2 to75 Micrometers by Optical Microscopy", ASTM Volume 14.02, 1993,incorporated herein by reference.

The particles may have a variety of shapes, including spherical,spheroidal, elliptical, lamellar, irregular, needle and rod-like,provided that the desired refractive index is provided. The particulatecan be in a variety of physical forms, including rutile, anatase or acombination thereof.

The compositions of the present invention preferably comprise from about0.1% to about 3% of the particulate material. Especially preferred aretopical compositions containing from about 0.3% to about 2%, morepreferably from about 0.5% to about 1%, of the particulate material.

The particulate material can be water-dispersible, oil-dispersible, or acombination thereof. Water- or oil- dispersibility may be inherent tothe particle or may be imparted by coating the particles with materialto impart a hydrophilic or hydrophobic surface property to theparticles. For example, hydrophilic coatings may comprise an amino acid,aluminum oxide or aluminum silicate. Exemplary hydrophobic coatings maycomprise organosilicone compounds or metal soaps such as aluminumstearate, aluminum laurate, and zinc stearate.

Inorganic particulate materials, e.g., comprising TiO₂, ZnO or ZrO₂ arecommercially available from a number of sources. Nonlimiting examples ofsuitable particulate materials are available from Warner Jenkinson(C-9729, a hydrophobic, dimethicone treated, anatase form TiO₂); U.S.Cosmetics (TRONOX TiO₂ series, e.g., AT-T-CR837, a hydrophilic, rutile,amino acid treated TiO₂ ; AT-T-328, a hydrophilic, anatase, amino acidtreated TiO₂ ; and SAT-T CR837, a rutile TiO₂); and Kobo (TRONOX TiO₂series, e.g., ST490, a rutile, silane treated TiO₂). The particulatematerials are available in essentially neat, powdered form orpredispersed in various types of dispersants, including but not limitedto isopropyl isostearate, isopropyl palmitate, methyl isostearate,Finsolv TN, cylcomethicone, and cyclomethicone and dimethiconecopolyols.

The compositions may contain other inorganic or organic particulatematerials, e.g., fillers or pigments, provided that they do notsignificantly reduce the benefits of the invention. For example, thetotal amount of all particulate material in the composition (includingthe above-described particulate having a refractive index of at leastabout 2 and any other particulate), by weight %, may be about 10 orless, about 5 or less, or about 3 or less. It is preferred that theparticulates in the compositions of the invention consist essentially ofthe particulate material described in this section entitled "ParticulateMaterial."

Carrier

The compositions of the present invention comprise a safe and effectiveamount of a dermatologically acceptable carrier within which theessential particulate material and optional other materials areincorporated to enable the particulate material and optional componentsto be delivered to the skin at an appropriate concentration. The carriercan thus act as a diluent, dispersant, solvent, or the like for theparticulate material which ensures that it can be applied to anddistributed evenly over the selected target at an appropriateconcentration.

The carrier may contain one or more dermatologically acceptable solid,semi-solid or liquid fillers, diluents, solvents, extenders and thelike. The carrier may be solid, semi-solid or liquid. Preferred carriersare substantially liquid. The carrier can itself be inert or it canpossess dermatological benefits of its own. Concentrations of thecarrier can vary with the carrier selected and the intendedconcentrations of the essential and optional components.

Suitable carriers include conventional or otherwise known carriers thatare dermatologically acceptable. The carrier should also be physicallyand chemically compatible with the essential components describedherein, and should not unduly impair stability, efficacy or other usebenefits associated with the compositions of the present invention.Preferred components of the compositions of this invention should becapable of being comingled in a manner such that there is no interactionwhich would substantially reduce the efficacy of the composition underordinary use situations.

The type of carrier utilized in the present invention depends on thetype of product form desired for the composition. The topicalcompositions useful in the subject invention may be made into a widevariety of product forms such as are known in the art. These include,but are not limited to, lotions, creams, gels, sticks, sprays,ointments, pastes, mousses and cosmetics (e.g., solid, semi-solid, orliquid make-up, including foundations, eye-makeup, pigmented ornon-pigmented lip treatments, e.g., lipsticks, and the like). Theseproduct forms may comprise several types of carriers including, but notlimited to, solutions, aerosols, emulsions, gels, solids, and liposomes.

Preferred carriers contain a dermatologically acceptable, hydrophilicdiluent. As used herein, "diluent" includes materials in which theparticulate material can be dispersed, dissolved, or otherwiseincorporated. Nonlimiting examples of hydrophilic diluents are water,organic hydrophilic diluents such as lower monovalent alcohols (e.g., C₁-C₄) and low molecular weight glycols and polyols, including propyleneglycol, polyethylene glycol (e.g., Molecular Weight 200-600 g/mole),polypropylene glycol (e.g., Molecular Weight 425-2025 g/mole), glycerol,butylene glycol, 1,2,4-butanetriol, sorbitol esters, 1,2,6-hexanetriol,ethanol, isopropanol, sorbitol esters, butanediol, ether propanol,ethoxylated ethers, propoxylated ethers and combinations thereof. Wateris a preferred diluent. The composition preferably comprises from about60% to about 99.99% of the hydrophilic diluent.

Solutions according to the subject invention typically include adermatologically acceptable hydrophilic diluent. Solutions useful in thesubject invention preferably contain from about 60% to about 99.99% ofthe hydrophilic diluent.

Aerosols according to the subject invention can be formed by adding apropellant to a solution such as described above. Exemplary propellantsinclude chloro-fluorinated lower molecular weight hydrocarbons.Additional propellants that are useful herein are described in Sagarin,Cosmetics Science and Technology 2nd Edition, Vol. 2, pp. 443-465(1972), incorporated herein by reference. Aerosols are typically appliedto the skin as a spray-on product.

Preferred carriers comprise an emulsion comprising a hydrophilic phasecomprising a hydrophilic component, e.g., water or other hydrophilicdiluent, and a hydrophobic phase comprising a hydrophobic component,e.g., a lipid, oil or oily material. As well known to one skilled in theart, the hydrophilic phase will be dispersed in the hydrophobic phase,or vice versa, to form respectively hydrophilic or hydrophobic dispersedand continuous phases, depending on the composition ingredients. Inemulsion technology, the term "dispersed phase" is a term well-known toone skilled in the art which means that the phase exists as smallparticles or droplets that are suspended in and surrounded by acontinuous phase. The dispersed phase is also known as the internal ordiscontinuous phase. The emulsion may be or comprise (e.g., in a tripleor other multi-phase emulsion) an oil-in-water emulsion or awater-in-oil emulsion such as a water-in-silicone emulsion. Oil-in-wateremulsions typically comprise from about 1% to about 50% (preferablyabout 1% to about 30%) of the dispersed hydrophobic phase and from about1% to about 98% (preferably from about 40% to about 90%) of thecontinuous hydrophilic phase; water-in-oil emulsions typically comprisefrom about 1% to about 98% (preferably from about 40% to about 90%) ofthe dispersed hydrophilic phase and from about 1% to about 50%(preferably about 1% to about 30%) of the continuous hydrophobic phase.The emulsion may also comprise a gel network, such as described in G. M.Eccleston, Application of Emulsion Stability Theories to Mobile andSemisolid O/W Emulsions, Cosmetics & Toiletries, Vol. 101, November1996, pp. 73-92, incorporated herein by reference. Preferred emulsionsare further described below.

The topical compositions of the subject invention, including but notlimited to lotions and creams, may comprise a dermatologicallyacceptable emollient. Such compositions preferably contain from about 2%to about 50% of the emollient. Emollients tend to lubricate the skin,increase the smoothness and suppleness of the skin, prevent or relievedryness of the skin, and/or protect the skin. Emollients are typicallywater-immiscible, oily or waxy materials. A wide variety of suitableemollients are known and may be used herein. Sagarin, Cosmetics, Scienceand Technology, 2nd Edition, Vol. 1, pp. 32-43 (1972), incorporatedherein by reference, contains numerous examples of materials suitable asan emollient.

Lotions and creams according to the present invention generally comprisea solution carrier system and one or more emollients. Lotions typicallycomprise from about 1% to about 20%, preferably from about 5% to about10%, of emollient; from about 50% to about 90%, preferably from about60% to about 80%, water. A cream typically comprises from about 5% toabout 50%, preferably from about 10% to about 20%, of emollient; andfrom about 45% to about 85%, preferably from about 50% to about 75%/,water.

Ointments of the present invention may comprise a simple carrier base ofanimal or vegetable oils or semi-solid hydrocarbons (oleaginous);absorption ointment bases which absorb water to form emulsions; or watersoluble carriers, e.g., a water soluble solution carrier. Ointments mayfurther comprise a thickening agent, such as described in Sagarin,Cosmetics, Science and Technology, 2nd Edition, Vol. 1, pp. 72-73(1972), incorporated herein by reference, and/or an emollient. Forexample, an ointment may comprise from about 2% to about 10% of anemollient; and from about 0.1% to about 2% of a thickening agent.

Compositions of this invention useful for cleansing ("cleansers") areformulated with a suitable carrier, e.g., as described above, andpreferably contain one or more dermatologically acceptable surfactantsin an amount which is safe and effective for cleansing. Preferredcompositions contain from about 1% to about 90%, more preferably fromabout 5% to about 10%, of a dermatologically acceptable surfactant. Thesurfactant is suitably selected from anionic, cationic, nonionic,zwitterionic, amphoteric and ampholytic surfactants, as well as mixturesof these surfactants. Such surfactants are well known to those skilledin the detergency art. Nonlimiting examples of possible surfactantsinclude isoceteth-20, sodium methyl cocoyl taurate, sodium methyl oleoyltaurate, sodium lauryl sulfate, and betaines such as described herein.See U.S. Pat. No. 4,800,197, to Kowcz et al., issued Jan. 24, 1989,which is incorporated herein by reference in its entirety, for exemplarysurfactants useful herein. Examples of a broad variety of additionalsurfactants useful herein are described in McCutcheon's Detergents andEmulsifiers, North American Edition (1986), published by AlluredPublishing Corporation, which is incorporated herein by reference in itsentirety. The cleansing compositions can optionally contain, at theirart-established levels, other materials which are conventionally used incleansing compositions.

The physical form of the cleansing compositions is not critical. Thecompositions can be, for example, formulated as toilet bars, liquids,shampoos, bath gels, hair conditioners, hair tonics, pastes, or mousses.Toilet bars are most preferred since this is the form of cleansing agentmost commonly used to wash the skin. Preferred rinse-off cleansingcompositions, such as shampoos, include a delivery system adequate todeposit sufficient levels of actives on the skin and scalp. A preferreddelivery system involves the use of insoluble complexes. For a morecomplete disclosure of such delivery systems, see U.S. Pat. No.4,835,148, Barford et al., issued May 30, 1989, incorporated herein byreference in its entirety.

As used herein, the term "foundation" refers to a liquid, semi-liquid,semi-solid, or solid skin cosmetic which includes, but is not limited tolotions, creams, gels, pastes, cakes, and the like. Typically thefoundation is used over a large area of the skin, such as over the face,to provide a particular look. Foundations are typically used to providean adherent base for color cosmetics such as rouge, blusher, powder andthe like, and tend to hide skin imperfections and impart a smooth, evenappearance to the skin. Foundations of the present invention include adermatologically acceptable carrier for the essential particulatematerial and may include conventional ingredients such as oils,colorants, pigments, emollients, fragrances, waxes, stabilizers, and thelike. Exemplary carriers and such other ingredients which are suitablefor use herein are described, for example, in copending patentapplication Ser. No. 08/430,961, filed on Apr. 28, 1995 in the names ofMarcia L. Canter, Brain D. Barford, and Brian D. Hofrichter,incorporated herein by reference.

The compositions of the present invention are preferably formulated tohave a pH of 10.5 or below. The pH values of these compositionspreferably range from about 2 to about 10.5, more preferably from about3 to about 8, even more preferably from about 5 to about 8.

Preferred compositions of this invention

Preferred topical compositions of the present invention comprise anemulsion. Emulsions of the present invention may contain one or more ofthe following:

a) Hydrophobic component

Emulsions according to the present invention contain a hydrophobic phasecomprising a lipid, oil, oily or other hydrophobic component. Thecompositions of the present invention preferably comprise from about 1%to about 50%, preferably from about 1% to about 30%, and more preferablyfrom about 1% to about 10% by weight of the composition of a hydrophobiccomponent. The hydrophobic component may be derived from animals,plants, or petroleum and may be natural or synthetic (i.e., man-made).Preferred hydrophobic components are substantially water-insoluble, morepreferably essentially water-insoluble. Preferred hydrophobic componentsare those having a melting point of about 25° C. or less under about oneatmosphere of pressure, and are suitable for conditioning the skin orhair.

Nonlimiting examples of suitable hydrophobic components include thoseselected from the group consisting of:

(1) Mineral oil, which is also known as petrolatum liquid, is a mixtureof liquid hydrocarbons obtained from petroleum. See The Merck Index,Tenth Edition, Entry 7048, p. 1033 (1983) and International CosmeticIngredient Dictionary, Fifth Edition, vol. 1, p.415-417 (1993), whichare incorporated by reference herein in their entirety.

(2) Petrolatum which is also known as petroleum jelly, is a colloidalsystem of nonstraight-chain solid hydrocarbons and high-boiling liquidhydrocarbons, in which most of the liquid hydrocarbons are held insidethe micelles. See The Merck Index, Tenth Edition, Entry 7047, p. 1033(1983); Schindler, Drug. Cosmet. Ind., 89, 36-37, 76, 78-80, 82 (1961);and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1,p. 537 (1993), which are incorporated by reference herein in theirentirety.

(3) Straight and branched chain hydrocarbons having from about 7 toabout 40 carbon atoms. Nonlimiting examples of these hydrocarbonmaterials include dodecane, isododecane, squalane, cholesterol,hydrogenated polyisobutylene, docosane (i.e. a C₂₂ hydrocarbon),hexadecane, isohexadecane (a commercially available hydrocarbon sold asPermethyl® 101A by Presperse, South Plainfield, N.J.). Also useful arethe C7-C40 isoparaffins, which are C7-C40 branched hydrocarbons.

(4) C1-C30 alcohol esters of C1-C30 carboxylic acids and of C2-C30dicarboxylic acids including straight and branched chain materials aswell as aromatic derivatives (as used herein in reference to thehydrophobic component, mono- and poly-carboxylic acids include straightchain, branched chain and aryl carboxylic acids). Nonlimiting examplesinclude diisopropyl sebacate, diisopropyl adipate, isopropyl myristate,isopropyl palmitate, methyl palmitate, myristyl propionate, 2-ethylhexylpalmitate, isodecyl neopentanoate, di-2-ethylhexyl maleate, cetylpalmitate, myristyl myristate, stearyl stearate, isopropyl stearate,methyl stearate, cetyl stearate, behenyl behenrate, dioctyl maleate,dioctyl sebacate, diisopropyl adipate, cetyl octanoate, diisopropyldilinoleate.

(5) mono-. di- and tri- glycerides of C1-C30 carboxylic acids, e.g.,caprilic/capric triglyceride, PEG-6 caprylic/capric triglyceride, PEG-8caprylic/capric triglyceride.

(6) alkylene glycol esters of C1-C30 carboxylic acids, e.g., ethyleneglycol mono -and di- esters, and propylene glycol mono- and di- estersof C1-C30 carboxylic acids e.g., ethylene glycol distearate.

(7) propoxylated and ethoxylated derivatives of the foregoing materials.

(8) C1-C30 mono- and poly- esters of sugars and related materials. Theseesters are derived from a sugar or polyol moiety and one or morecarboxylic acid moieties. Depending on the constituent acid and sugar,these esters can be in either liquid or solid form at room temperature.Examples of liquid esters include: glucose tetraoleate, the glucosetetraesters of soybean oil fatty acids (unsaturated), the mannosetetraesters of mixed soybean oil fatty acids, the galactose tetraestersof oleic acid, the arabinose tetraesters of linoleic acid, xylosetetralinoleate, galactose pentaoleate, sorbitol tetraoleate, thesorbitol hexaesters of unsaturated soybean oil fatty acids, xylitolpentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrosehexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixturesthereof. Examples of solid esters include: sorbitol hexaester in whichthe carboxylic acid ester moieties are palmitoleate and arachidate in a1:2 molar ratio; the octaester of raffinose in which the carboxylic acidester moieties are linoleate and behenate in a 1:3 molar ratio; theheptaester of maltose wherein the esterifying carboxylic acid moietiesare sunflower seed oil fatty acids and lignocerate in a 3:4 molar ratio;the octaester of sucrose wherein the esterifying carboxylic acidmoieties are oleate and behenate in a 2:6 molar ratio; and the octaesterof sucrose wherein the esterifying carboxylic acid moieties are laurate,linoleate and behenate in a 1:3:4 molar ratio. A preferred solidmaterial is sucrose polyester in which the degree of esterification is7-8, and in which the fatty acid moieties are C18 mono- and/ordi-unsaturated and behenic, in a molar ratio of unsaturates:behenic of1:7 to 3:5. A particularly preferred solid sugar polyester is theoctaester of sucrose in which there are about 7 behenic fatty acidmoieties and about 1 oleic acid moiety in the molecule. Other materialsinclude cottonseed oil or soybean oil fatty acid esters of sucrose. Theester materials are further described in, U.S. Pat. No. 2,831,854, U.S.Pat. No. 4,005,196, to Jandacek, issued Jan. 25, 1977; U.S. Pat. No.4,005,195, to Jandacek, issued Jan. 25, 1977, U.S. Pat. No. 5,306,516,to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,306,515, toLetton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,305,514, to Lettonet al., issued Apr. 26, 1994; U.S. Pat. No. 4,797,300, to Jandacek etal., issued Jan. 10, 1989; U.S. Pat. No. 3,963,699, to Rizzi et al,issued Jun. 15, 1976; U.S. Pat. No. 4,518,772, to Volpenhein, issued May21, 1985; and U.S. Pat. No. 4,517,360, to Volpenhein, issued May 21,1985; all of which are incorporated by reference herein in theirentirety.

9) Organopolysiloxane oils. The organopolysiloxane oil may be volatile,nonvolatile, or a mixture of volatile and non-volatile silicones. Theterm "nonvolatile" as sed in this context refers to those silicones thatare liquid under ambient conditions and have a flash point (under oneatmospheric of pressure) of or greater than about 100° C. The term"volatile" as used in this context refers to all other silicone oils.Suitable organopolysiloxanes can be selected from a wide variety ofsilicones spanning a broad range of volatilities and viscosities.Nonvolatile polysiloxanes are preferred. Nonlimiting examples ofsuitable silicones are disclosed in U.S. Pat. No. 5,069,897, to Orr,issued Dec. 3, 1991, which is incorporated by reference herein in itsentirety. Examples of suitable organopolysiloxane oils includepolyalkylsiloxanes, cyclic polyalkylsiloxanes, andpolyalkylarylsiloxanes.

Polyalkylsiloxanes useful in the composition herein includepolyalkylsiloxanes with viscosities of from about 0.5 to about 1,000,000centistokes at 25° C. Such polyalkylsiloxanes can be represented by thegeneral chemical formula R₃ SiO[R₂ SiO]_(x) SiR₃ wherein R is an alkylgroup having from one to about 30 carbon atoms (preferably R is methylor ethyl, more preferably methyl; also mixed alkyl groups can be used inthe same molecule), and x is an integer from 0 to about 10,000, chosento achieve the desired molecular weight which can range to over about10,000,000. Commercially available polyalkylsiloxanes include thepolydimethylsiloxanes, which are also known as dimethicones, examples ofwhich include the Vicasil® series sold by General Electric Company andthe Dow Corning® 200 series sold by Dow Corning Corporation. Specificexamples of suitable polydimethylsiloxanes include Dow Corning® 200fluid having a viscosity of 0.65 centistokes and a boiling point of 100°C., Dow Corning® 225 fluid having a viscosity of 10 centistokes and aboiling point greater than 200° C., and Dow Corning® 200 fluids havingviscosities of 50, 350, and 12,500 centistokes, respectively, andboiling points greater than 200° C. Suitable dimethicones include thoserepresented by the chemical formula (CH₃)₃ SiO[(CH₃)₂ SiO]_(x) [CH₃RSiO]_(y) Si(CH₃)₃ wherein R is straight or branched chain alkyl havingfrom two to about 30 carbon atoms and x and y are each integers of 1 orgreater selected to achieve the desired molecular weight which can rangeto over about 10,000,000. Examples of these alkyl-substituteddimethicones include cetyl dimethicone and lauryl dimethicone.

Cyclic polyalkylsiloxanes suitable for use in the composition includethose represented by the chemical formula [SiR₂ -O]_(n) wherein R is analkyl group (preferably R is methyl or ethyl, more preferably methyl)and n is an integer from about 3 to about 8, more preferably n is aninteger from about 3 to about 7, and most preferably n is an integerfrom about 4 to about 6. When R is methyl, these materials are typicallyreferred to as cyclomethicones. Commercially available cyclomethiconesinclude Dow Corning® 244 fluid having a viscosity of 2.5 centistokes,and a boiling point of 172° C., which primarily contains thecyclomethicone tetramer (i.e. n=4), Dow Corning® 344 fluid having aviscosity of 2.5 centistokes and a boiling point of 178° C., whichprimarily contains the cyclomethicone pentamer (i.e. n=5), Dow Corning®245 fluid having a viscosity of 4.2 centistokes and a boiling point of205° C., which primarily contains a mire of the cyclomethicone tetramerand pentamer (i.e. n=4 and 5), and Dow Corning® 345 fluid having aviscosity of 4.5 centistokes and a boiling point of 217°, whichprimarily contains a mixture of the cyclomethicone tetramer, pentamer,and hexamer (i.e. n=4, 5, and 6).

Also useful are materials such as trimethylsiloxysilicate, which is apolymeric material corresponding to the general chemical formula [(CH₂)₃SiO_(1/2) ]_(x) [SiO₂ ]y, wherein x is an integer from about 1 to about500 and y is an integer from about 1 to about 500. A commerciallyavailable trimethylsiloxysilicate is sold as a mixture with dimethiconeas Dow Corning® 593 fluid.

Dimethiconols are also suitable for use in the composition. Thesecompounds can be represented by the chemical formulas R₃ SiO[R₂ SiO]_(x)SiR₂ OH and HOR₂ SiO[R₂ SiO]_(x) SiR₂ OH wherein R is an alkyl group(preferably R is methyl or ethyl, more preferably methyl) and x is aninteger from 0 to about 500, chosen to achieve the desired molecularweight. Commercially available dimethiconols are typically sold asmixtures with dimethicone or cyclomethicone (e.g. Dow Corning® 1401,1402, and 1403 fluids).

Polyalkylaryl siloxanes are also suitable for use in the composition.Polymethylphenyl siloxanes having viscosities from about 15 to about 65centistokes at 25° C. are especially useful.

Preferred for use herein are organopolysiloxanes selected from the groupconsisting of polyalkylsiloxanes, alkyl substituted dimethicones,cyclomethicones, trimethylsiloxysilicates, dimethiconols, polyalkylarylsiloxanes, and mixtures thereof. More preferred for use herein arepolyalkylsiloxanes and cyclomethicones. Preferred among thepolyalkylsiloxanes are dimethicones.

(10) Vegetable oils and hydrogenated vegetable oils. Examples ofvegetable oils and hydrogenated vegetable oils include safflower oil,castor oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil,palm oil, peanut oil, soybean oil, rapeseed oil, linseed oil, rice branoil, pine oil, sesame oil, sunflower seed oil, hydrogenated saffloweroil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenatedcottonseed oil, hydrogenated menhaden oil, hydrogenated palm kernel oil,hydrogenated palm oil, hydrogenated peanut oil, hydrogenated soybeanoil, hydrogenated rapeseed oil, hydrogenated linseed oil, hydrogenatedrice bran oil, hydrogenated sesame oil, hydrogenated sunflower seed oil,and mixtures thereof.

(11) animal fats and oils, e.g., lanolin and derivatives thereof, codliver oil.

(12) Also useful are C4-C20 alkyl ethers of polypropylene glycols,C1-C20 carboxylic acid esters of polypropylene glycols, and di-C8-C30alkyl ethers. Nonlimiting examples of these materials include PPG-14butyl ether, PPG-15 stearyl ether, dioctyl ether, dodecyl octyl ether,and mixtures thereof.

b) Hydrophilic component

Emulsions of the present invention also comprise a hydrophiliccomponent, e.g., water or other hydrophilic diluent. The hydrophilicphase can thus comprise water, or a combination of water and one or morewater soluble or dispersible ingredients. Hydrophilic componentscomprising water are preferred.

(c) Other components

Emulsions and other topical compositions of the present invention maycomprise a variety of other ingredients such as disclosed herein. Aswill be understood by the skilled artisan, a given component willdistribute primarily into either a hydrophilic phase or hydrophobicphase, depending on the hydrophilicity of the component in thecomposition.

Emulsions of the present invention preferably include one or morecompounds selected from emulsifiers, surfactants, structuring agents,and thickeners. Compositions containing these ingredients tend to havethe preferred apparent viscosities described herein.

(1) Emulsifiers/Surfactants

The emulsion may contain an emulsifier and/or surfactant, generally tohelp disperse and suspend the discontinuous phase within the continuousphase. A wide variety of such agents can be employed. Known orconventional emulsifiers/surfactants can be used in the composition,provided that the selected agent is chemically and physically compatiblewith essential components of the composition, and provides the desireddispersion characteristics. Suitable agents includenon-silicone-containing emulsifiers/surfactants, siliconeemulsifiers/surfactants, and mixtures thereof.

In a preferred embodiment, the composition comprises a hydrophilicemulsifier or surfactant. The compositions of the present inventionpreferably comprise from about 0.05% to about 5%, more preferably fromabout 0.05% to about 1% of at least one hydrophilic surfactant. Withoutintending to be limited by theory, it is believed that the hydrophilicsurfactant assists in dispersing hydrophobic materials, e.g.,hydrophobic structuring agents, in the hydrophilic phase. Thesurfactant, at a minimum, must be hydrophilic enough to disperse in thehydrophilic phase. Preferred surfactants are those having an HLB of atleast about 8. The exact surfactant chosen will depend upon the pH ofthe composition and the other components present.

Preferred hydrophilic surfactants are selected from nonionicsurfactants. Among the nonionic surfactants that are useful herein arethose that can be broadly defined as condensation products of long chainalcohols, e.g. C8-30 alcohols, with sugar or starch polymers, i.e.,glycosides. These compounds can be represented by the formula (S)_(n)-O-R wherein S is a sugar moiety such as glucose, fructose, mannose, andgalactose; n is an integer of from about 1 to about 1000, and R is aC8-30 alkyl group. Examples of long chain alcohols from which the alkylgroup can be derived include decyl alcohol, cetyl alcohol, stearylalcohol, lauryl alcohol, myristyl alcohol, oleyl alcohol, and the like.Preferred examples of these surfactants include those wherein S is aglucose moiety, R is a C8-20 alkyl group, and n is an integer of fromabout 1 to about 9. Commercially available examples of these surfactantsinclude decyl polyglucoside (available as APG 325 CS from Henkel) andlauryl polyglucoside (available as APG 600 CS and 625 CS from Henkel).

Other useful nonionic surfactants include the condensation products ofalkylene oxides with fatty acids (i.e. alkylene oxide esters of fattyacids). These materials have the general formula RCO(X)_(n) OH wherein Ris a C10-30 alkyl group, X is --OCH₂ CH₂ -- (i.e. derived from ethyleneglycol or oxide) or --OCH₂ CHCH₃ -- (i.e. derived from propylene glycolor oxide), and n is an integer from about 6 to about 200. Other nonionicsurfactants are the condensation products of alkylene oxides with 2moles of fatty acids (i.e. alkylene oxide diesters of fatty acids).These materials have the general formula RCO(X)_(n) OOCR wherein R is aC10-30 allyl group, X is --OCH₂ CH₂ --(i.e. derived from ethylene glycolor oxide) or --OCH₂ CHCH₃ --(i.e. derived from propylene glycol oroxide), and n is an integer from about 6 to about 100. Other nonionicsurfactants are the condensation products of alkylene oxides with fattyalcohols (i.e. alkylene oxide ethers of fatty alcohols). These materialshave the general formula R(X)_(n) OR' wherein R is a C10-30 alkyl group,X is --OCH₂ CH₂ --(i.e. derived from ethylene glycol or oxide) or --OCH₂CHCH₃ -- (i.e. derived from propylene glycol or oxide), and n is aninteger from about 6 to about 100 and R' is H or a C10-30 alkyl group.Still other nonionic surfactants are the condensation products ofalkylene oxides with both fatty acids and fatty alcohols [i.e. whereinthe polyalkylene oxide portion is esterified on one end with a fattyacid and etherified (i.e. connected via an ether linkage) on the otherend with a fatty alcohol]. These materials have the general formulaRCO(X)_(n) OR' wherein R and R' are C10-30 alkyl groups, X is --OCH₂ CH₂(i.e. derived from ethylene glycol or oxide) or --OCH₂ CHCH₃ -- (derivedfrom propylene glycol or oxide), and n is an integer from about 6 toabout 100.

Nonlimiting examples of these alkylene oxide derived nonionicsurfactants include ceteth-6, ceteth-10, ceteth-12, ceteareth-6,ceteareth-10, ceteareth-12, steareth-6, steareth-10, steareth-12, PEG-6stearate, PEG-10 stearate, PEG-100 stearate, PEG-12 stearate, PEG-20glyceryl stearate, PEG-80 glyceryl tallowate, PEG-10 glyceryl stearate,PEG-30 glyceryl cocoate, PEG-80 glyceryl cocoate, PEG-200 glyceryltallowate, PEG-8 dilaurate, PEG-10 distearate, and mixtures thereof.

Still other useful nonionic surfactants include polyhydroxy fatty acidamide surfactants corresponding to the structural formula: ##STR1##wherein: R¹ is H, C₁ -C₄ alkyl, 2-hydroxyethyl, 2-hydroxy- propyl,preferably C₁ -C₄ 10 alkyl, more preferably methyl or ethyl, mostpreferably methyl; R is C₅ -C₃₁ alkyl or alkenyl, preferably C₇ -C₁₉alkyl or alkenyl, more preferably C₉ -C₁₇ alkyl or alkenyl, mostpreferably C₁₁ -C₁₅ alkyl or alkenyl; and Z is a polhydroxyhydrocarbylmoiety having a linear hydrocarbyl chain with a least 3 hydroxylsdirectly connected to the echain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably is asugar moiety selected from the group consisting of glucose, fructose,maltose, lactose, galactose, mannose, xylose, and mixtures thereof. Anespecially preferred surfactant corresponding to the above structure iscoconut alkyl N-methyl glucoside amide (i.e., wherein the R² CO-- moietyis derived from coconut oil fatty acids). Processes for makingcompositions containing polyhydroxy fatty acid amides are disclosed, forexample, in G.B. Patent Specification 809,060, published Feb. 18, 1959,by Thomas Hedley & Co., Ltd.; U.S. Pat. No. 2,965,576, to E. R Wilson,issued Dec. 20, 1960; U.S. Pat. No. 2,703,798, to A. M. Schwartz, issuedMar. 8, 1955; and U.S. Pat. No. 1,985,424, to Piggott, issued Dec. 25,1934; which are incorporated herein by reference in their entirety.

Preferred among the nonionic surfactants are those selected from thegroup consisting of steareth-21, ceteareth-20, ceteareth-12, sucrosecocoate, steareth-100, PEG-100 stearate, and mixtures thereof.

Other nonionic surfactants suitable for use herein include sugar estersand polyesters, alkoxylated sugar esters and polyesters, C1-C30 fattyacid esters of C1-C30 fatty alcohols, alkoxylated derivatives of C1-C30fatty acid esters of C1-C30 fatty alcohols, alkoxylated ethers of C1-C30fatty alcohols, polyglyceryl esters of C1-C30 fatty acids, C1-C30 estersof polyols, C1-C30 ethers of polyols, alkyl phosphates, polyoxyalkylenefatty ether phosphates, fatty acid amides, acyl lactylates, and mixturesthereof. Nonlimiting examples of these non-silicon-containingemulsifiers include: polyethylene glycol 20 sorbitan monolauratePolysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20,Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth-10,Polysorbate 80, cetyl phosphate, potassium cetyl phosphate,diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate,polyoxyethylene 20 sorbitan trioleate (Polysorbate 85), sorbitanmonolaurate, polyoxyethylene 4 lauryl ether sodium stearate,polyglyceryl-4 isostearate, hexyl laurate, PPG-2 methyl glucose etherdistearate, PEG-100 stearate, and mixtures thereof.

Another emulsifier useful herein are fatty acid ester blends based on amixture of sorbitan or sorbitol fatty acid ester and sucrose fatty acidester, the fatty acid in each instance being preferably C₈ -C₂₄, morepreferably C₁₀ -C₂₀. The preferred fatty acid ester emulsifier is ablend of sorbitan or sorbitol C₁₆ -C₂₀ fatty acid ester with sucrose C₁₀-C₁₆ fatty acid ester, especially sorbitan stearate and sucrose cocoate.This is commercially available from ICI under the trade name Arlatone2121.

The hydrophilic surfactants useful herein can alternatively oradditionally include any of a wide variety of cationic, anionic,zwitterionic, and amphoteric surfactants such as are known in the art.See, e.g., McCutcheon's, Detergents and Emulsifiers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Pat.No. 5,011,681 to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No.4,421,769 to Dixon et al., issued Dec. 20, 1983; and U.S. Pat. No.3,755,560 to Dickert et al., issued Aug. 28, 1973; these four referencesare incorporated herein by reference in their entirety.

Exemplary cationic surfactants useful herein include those disclosed inU.S. Pat. No. 5,151,209, to McCall et al., issued Sep. 29, 1992; U.S.Pat. No. 5,151,210, to Steuri et al., issued Sep. 29, 1992; U.S. Pat.No. 5,120,532, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.4,387,090, to Bolich, issued Jun. 7, 1983;; U.S. Patent 3,155,591,Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678, to Laughlin etal., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, to Bailey et al.,issued May 25, 1976; McCutcheon's, Detergents & Emulsifiers, (NorthAmerican edition 1979) M.C. Publishing Co.; and Schwartz, et al.,Surface Active Agents Their Chemistry and Technology, New York:Interscience Publishers, 1949; all of these documents being incorporatedherein by reference in their entirety. The cationic surfactants usefulherein include cationic ammonium salts such as quaternary ammoniumsalts, and amino-amides.

A wide variety of anionic surfactants are also useful herein. See, e.g.,U.S. Pat. No. 3,929,678, to Laughlin et al., issued Dec. 30, 1975, whichis incorporated herein by reference in its entirety. Nonlimitingexamples of anionic surfactants include the alkoyl isethionates (e.g.,C₁₂ -C₃₀), allyl and alkyl ether sulfates and salts thereof, alkyl andallyl ether phosphates and salts thereof, alkyl methyl taurates (e.g.,C₁₂ -C₃₀), and soaps (e.g., alkali metal salts, e.g., sodium orpotassium salts) of fatty acids.

Amphoteric and zwitterionic surfactants are also useful herein. Examplesof amphoteric and zwitterionic surfactants which can be used in thecompositions of the present invention are those which are broadlydescribed as derivatives of aliphatic secondary and tertiary amines inwhich the aliphatic radical can be straight or branched chain andwherein one of the aliphatic substituents contains from about 8 to about22 carbon atoms (preferably C₈ -C₁₈) and one contains an anionic watersolubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate. Examples are alkyl imino acetates, and iminodialkanoatesand aminoalkanoates, imidazolinium and ammonium derivatives. Othersuitable amphoteric and zwitterionic surfactants are those selected fromthe group consisting of betaines, sultaines, hydroxysultaines, alkylsarcosinates (e.g., C₁₂ -C₃₀), and alkanoyl sarcosinates.

Preferred emulsions of the present invention include a siliconecontaining emulsifier or surfactant. A wide variety of siliconeemulsifiers are useful herein. These silicone emulsifiers are typicallyorganically modified organopolysiloxanes, also known to those skilled inthe art as silicone surfactants. Useful silicone emulsifiers includedimethicone copolyols. These materials are polydimethyl siloxanes whichhave been modified to include polyether side chains such as polyethyleneoxide chains, polypropylene oxide chains, mixtures of these chains, andpolyether chains containing moieties derived from both ethylene oxideand propylene oxide. Other examples include allyl-modified dimethiconecopolyols, i.e., compounds which contain C2-C30 pendant side chains.Still other useful dimethicone copolyols include materials havingvarious cationic, anionic, amphoteric, and zwitterionic pendantmoieties.

The dimethicone copolyol emulsifiers useful herein can be described bythe following general structure: ##STR2## wherein R is C1-C30 straight,branched, or cyclic allyl and R² is selected from the group consistingof

    --(CH.sub.2).sub.n --O--(CH.sub.2 CHR.sup.3 O).sub.m --H,

and

    --(CH.sub.2).sub.n --O--(CH.sub.2 CHR.sup.3 O).sub.m --(CH.sub.2 CHR.sup.4 O).sub.o --H,

wherein n is an integer from 3 to about 10; R³ and R⁴ are selected fromthe group consisting of H and C1-C6 straight or branched chain alkylsuch that R³ and R⁴ are not simultaneously the same; and m, o, x, and yare selected such that the molecule has an overall molecular weight fromabout 200 to about 10,000,000, with m, o, x, and y being independentlyselected from integers of zero or greater such that m and o are not bothsimultaneously zero, and z being independently selected from integers of1 or greater. It is recognized that positional isomers of thesecopolyols can be achieved. The chemical representations depicted abovefor the R² moieties containing the R³ and R⁴ groups are not meant to belimiting but are shown as such for convenience.

Also useful herein, although not strictly classified as dimethiconecopolyols, are silicone surfactants as depicted in the structures in theprevious paragraph wherein R² is:

    --CH.sub.2).sub.n --O--R.sup.5,

wherein R⁵ is a cationic, anionic, amphoteric, or zwitterionic moiety.

Nonlimiting examples of dimethicone copolyols and other siliconesurfactants useful as emulsifiers herein include polydimethylsiloxanepolyether copolymers with pendant polyethylene oxide sidechains,polydimethylsiloxane polyether copolymers with pendant polypropyleneoxide sidechains, polydimethylsiloxane polyether copolymers with pendantmixed polyethylene oxide and polypropylene oxide sidechains,polydimethylsiloxane polyether copolymers with pendant mixedpoly(ethylene)(propylene)oxide sidechains, polydimethylsiloxanepolyether copolymers with pendant organobetaine sidechains,polydimethylsiloxane polyether copolymers with pendant carboxylatesidechains, polydimethylsiloxane polyether copolymers with pendantquaternary ammonium sidechains; and also further modifications of thepreceding copolymers containing pendant C2-C30 straight, branched, orcyclic alkyl moieties. Examples of commercially available dimethiconecopolyols useful herein sold by Dow Corning Corporation are Dow Corning®190, 193, Q2-5220, 2501 Wax, 2-5324 fluid, and 3225C (this latermaterial being sold as a mixture with cyclomethicone). Cetyl dimethiconecopolyol is commercially available as a mixture with polyglyceryl-4isostearate (and) hexyl laurate and is sold under the tradename ABIL®WE-09 (available from Goldschmidt). Cetyl dimethicone copolyol is alsocommercially available as a mixture with hexyl laurate (and)polyglyceryl-3 oleate (and) cetyl dimethicone and is sold under thetradename ABIL® WS-08 (also available from Goldschmidt). Othernonimiting examples of dimethicone copolyols also include lauryldimethicone copolyol, dimethicone copolyol acetate, dimethicone copolyoladipate, dimethicone copolyolamine, dimethicone copolyol behenate,dimethicone copolyol butyl ether, dimethicone copolyol hydroxy stearate,dimethicone copolyol isostearate, dimethicone copolyol laurate,dimethicone copolyol methyl ether, dimethicone copolyol phosphate, anddimethicone copolyol stearate. See International Cosmetic IngredientDictionary, Fifth Edition, 1993, which is incorporated by referenceherein in its entirety.

Dimethicone copolyol emulsifiers useful herein are described, forexample, in U.S. Pat. No. 4,960,764, to Figueroa, Jr. et al., issuedOct. 2, 1990; European Pat. No. EP 330,369, to SaNogueira, publishedAug. 30, 1989; G. H. Dahms, et al., "New Formulation PossibilitiesOffered by Silicone Copolyols," Cosmetics & Toiletries, vol. 110, pp.91-100, March 1995; M. E. Carlotti et al., "Optimization of W/O-SEmulsions And Study Of The Quantitative Relationships Between EsterStructure And Emulsion Properties," J. Dispersion Science AndTechnology, 13(3), 315-336 (1992); P. Hameyer, "ComparativeTechnological Investigations of Organic and Organosilicone Emulsifiersin Cosmetic Water-in-Oil Emulsion Preparations," HAPPI 28(4), pp. 88-128(1991); J. Smid-Korbar et al., "Efficiency and usability of siliconesurfactants in emulsions," Provisional Communication, InternationalJournal of Cosmetic Science, 12, 135-139 (1990); and D. G. Krzysik etal., "A New Silicone Emulsifier For Water-in-Oil Systems," Drug andCosmetic Industry vol. 146(4) pp. 28-81 (April 1990); incorporated byreference herein in their entirety.

(2) Structuring Agent

The compositions hereof, and especially the emulsions hereof, maycontain a structuring agent. Structuring agents are particularlypreferred in the oil-in-water emulsions of the present invention.Without being limited by theory, it is believed that the structuringagent assists in providing rheological characteristics to thecomposition which contribute to the stability of the composition. Forexample, the structuring agent tends to assist in the formation of theliquid crystalline gel network structures. The structuring agent mayalso function as an emulsifier or surfactant. Preferred compositions ofthis invention comprise from about 1% to about 20%, more preferably fromabout 1% to about 10%, most preferably from about 2% to about 9%, of oneor more structuring agents.

Preferred structuring agents are those having an HLB of from about 1 toabout 8 and having a melting point of at least about 45° C. Suitablestructuring agents are those selected from the group consisting ofsaturated C₁₄ to C₃₀ fatty alcohols, saturated C₁₆ to C₃₀ fatty alcoholscontaining from about 1 to about 5 moles of ethylene oxide, saturatedC₁₆ to C₃₀ diols, saturated C₁₆ to C₃₀ monoglycerol ethers, saturatedC₁₆ to C₃₀ hydroxy fatty acids, C₁₄ to C₃₀ hydroxylated andnonhydroxylated saturated fatty acids, C₁₄ to C₃₀ saturated ethoxylatedfatty acids, amines and alcohols containing from about 1 to about 5moles of ethylene oxide diols, C₁₄ to C₃₀ saturated glyceryl mono esterswith a monoglyceride content of at least 40%, C₁₄ to C₃₀ saturatedpolyglycerol esters having from about 1 to about 3 alkyl group and fromabout 2 to about 3 saturated glycerol units, C₁₄ to C₃₀ glyceryl monoethers, C₁₄ to C₃₀ sorbitan mono/diesters, C₁₄ to C₃₀ saturatedethoxylated sorbitan mono/diesters with about 1 to about 5 moles ofethylene oxide, C₁₄ to C₃₀ saturated methyl glucoside esters, C₁₄ to C₃₀saturated sucrose mono/diesters, C₁₄ to C₃₀ saturated ethoxylated methylglucoside esters with about 1 to about 5 moles of ethylene oxide, C₁₄ toC₃₀ saturated polyglucosides having an average of between 1 to 2 glucoseunits and mixtures thereof, having a melting point of at least about 45°C.

The preferred structuring agents of the present invention are selectedfrom the group consisting of stearic acid, palmitic acid, stearylalcohol, cetyl alcohol, behenyl alcohol, stearic acid, palmitic acid,the polyethylene glycol ether of stearyl alcohol having an average ofabout 1 to about 5 ethylene oxide units, the polyethylene glycol etherof cetyl alcohol having an average of about 1 to about 5 ethylene oxideunits, and mixtures thereof. More preferred structuring agents of thepresent invention are selected from the group consisting of stearylalcohol, cetyl alcohol, behenyl alcohol, the polyethylene glycol etherof stearyl alcohol having an average of about 2 ethylene oxide units(steareth-2), the polyethylene glycol ether of cetyl alcohol having anaverage of about 2 ethylene oxide units, and mixtures thereof. Even morepreferred structuring agents are selected from the group consisting ofstearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenylalcohol, steareth-2, and mixtures thereof.

(3) Thickening Agent (including thickeners and gelling agents)

The compositions of the present invention can also comprise a thickeningagent, preferably from about 0.1% to about 5%, more preferably fromabout 0.1% to about 3%, and most preferably from about 0.25% to about2%, of a thickening agent.

Nonlimiting classes of thickening agents include those selected from thegroup consisting of:

(i) Carboxylic Acid Polymers

These polymers are crosslinked compounds containing one or more monomersderived from acrylic acid, substituted acrylic acids, and salts andesters of these acrylic acids and the substituted acrylic acids, whereinthe crosslinking agent contains two or more carbon-carbon double bondsand is derived from a polyhydric alcohol. The preferred carboxylic acidpolymers are of two general types. The first type of polymer is acrosslinked homopolymer of an acrylic acid monomer or derivative thereof(e.g., wherein the acrylic acid has substituents on the two and threecarbon positions independently selected from the group consisting ofC₁₋₄ alkyl, --CN, --COOH, and mixtures thereof). The second type ofpolymer is a crosslinked copolymer having a first monomer selected fromthe group consisting of an acrylic acid monomer or derivative thereof(as just described in the previous sentence), a short chain alcohol(i.e., a C₁₋₄) acrylate ester monomer or derivative thereof (e.g.,wherein the acrylic acid portion of the ester has substituents on thetwo and three carbon positions independently selected from the groupconsisting of C₁₋₄ alkyl, --CN, --COOH and mixtures thereof), andmixtures thereof, and a second monomer which is a long chain alcohol(i.e. C₈₋₄₀) acrylate ester monomer or derivative thereof (e.g., whereinthe acrylic acid portion of the ester has substituents on the two andthree carbon positions independently selected from the group consistingof C₁₋₄ alkyl, --CN, --COOH, and mixtures thereof). Combinations ofthese two types of polymers are also useful herein.

In the first type of crosslinked homopolymers, the monomers arepreferably selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylicacid being most preferred. In the second type of crosslinked copolymersthe acrylic acid monomer or derivative thereof is preferably selectedfrom the group consisting of acrylic acid, methacrylic acid, ethacrylicacid, and mixtures thereof, with acrylic acid, methacrylic acid, andmixtures thereof being most preferred. The short chain alcohol acrylateester monomer or derivative thereof is preferably selected from thegroup consisting of C₁₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, C₁₋₄ alcohol ethacrylate esters, and mixturesthereof, with the C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, and mixtures thereof, being most preferred. Thelong chain alcohol acrylate ester monomer is selected from C₈₋₄₀ alkylacrylate esters, with C₁₀₋₃₀ alkyl acrylate esters being preferred.

The crosslinking agent in both of these types of polymers is apolyalkenyl polyether of a polyhydric alcohol containing more than onealkenyl ether group per molecule, wherein the parent polyhydric alcoholcontains at least 3 carbon atoms and at least 3 hydroxyl groups.Preferred crosslinkers are those selected from the group consisting ofallyl ethers of sucrose and allyl ethers of pentaerythritol, andmixtures thereof. These polymers useful in the present invention aremore fully described in U.S. Pat. No. 5,087,445, to Haffey et al.,issued Feb. 11, 1992; U.S. Pat. No. 4,509,949, to Huang et al., issuedApr. 5, 1985; U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957;which are both incorporated by reference herein in their entirety. Seealso, CTFA International Cosmetic Ingredient Dictionary, fourth edition,1991, pp. 12 and 80; which are also incorporated herein by reference intheir entirety.

Examples of commercially available homopolymers of the first type usefulherein include the carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol® 900 series from B. F. Goodrich(e.g., Carbopol® 954). Examples of commercially available copolymers ofthe second type useful herein include copolymers of C₁₀₋₃₀ alkylacrylates with one or more monomers of acrylic acid, methacrylic acid,or one of their short chain (i.e. C₁₋₄ alcohol) esters, wherein thecrosslinking agent is an allyl ether of sucrose or pentaerytritol. Thesecopolymers are known as acrylates/CIO-30 alkyl acrylate crosspolymersand are commercially available as Carbopol® 1342, Carbopol® 1382PemulenTR-1, and Pemulen TR-2, from B. F. Goodrich. In other words, examples ofcarboxylic acid polymer thickeners useful herein are those selected fromthe group consisting of carbomers, acrylates/C10-C30 alkyl acrylatecrosspolymers, and mixtures thereof.

(ii) Crosslinked Polyacrylate Polymers

The crosslinked polyacrylate polymers useful as thickeners or gellingagents include both cationic and nonionic polymers, with the cationicsbeing generally preferred. Examples of useful crosslinked nonionicpolyacrylate polymers and crosslinked cationic polyacrylate polymers arethose described in U.S. Pat. No. 5,100,660, to Hawe et al., issued Mar.31, 1992; U.S. Pat. No. 4,849,484, to Heard, issued Jul. 18, 1989; U.S.Pat. No. 4,835,206, to Farrar et al., issued May 30, 1989; U.S. Pat. No.4,628,078 to Glover et al. issued Dec. 9, 1986; U.S. Pat. No. 4,599,379to Flesher et al. issued Jul. 8, 1986; and EP 228,868, to Farrar et al.,published Jul. 15, 1987; all of which are incorporated by referenceherein in their entirety.

The crosslinked polyacrylate polymers are high molecular weightmaterials that can be characterized by the general formula: (A)_(l)(B)_(m) (C)_(n) and comprise the monomer units (A)_(l), (B)_(m), and(C)_(n), wherein (A) is a dialkylaminoalkyl acrylate monomer or itsquaternary ammonium or acid addition salt, (13) is a dialkylaminoalkylmethacrylate monomer or its quaternary ammonium or acid addition salt,(C) is a monomer that is polymerizable with (A) or (B), for example amonomer having a carbon-carbon double bond or other such polymerizablefunctional group, I is an integer of 0 or greater, m is an integer of 0or greater, n is an integer of 0 or greater, but where either l or m, orboth, must be 1 or greater.

The (C) monomer can be selected from any of the commonly used monomers.Nonlimiting examples of these monomers include ethylene, propylene,butylene, isobutylene, eicosene, maleic anhydride, acrylamide,methacrylamide, maleic acid, acrolein, cyclohexene, ethyl vinyl ether,and methyl vinyl ether. In the cationic polymers of the presentinvention, (C) is preferably acrylamide. The alkyl portions of the (A)and (B) monomers are short chain length alkyls such as C₁ -C₈,preferably C₁ -C₅, more preferably C₁ -C₃, and most preferably C₁ -C₂.When quaternized, the polymers are preferably quaternized with shortchain alkyls, i.e., C₁ -C₈, preferably C₁ -C₅, more preferably C₁ -C₃,and most preferably C₁ -C₂. The acid addition salts refer to polymershaving protonated amino groups. Acid addition salts can be performedthrough the use of halogen (e.g. chloride), acetic, phosphoric, nitric,citric, or other acids.

These (A)_(l) (B)_(m) (C)_(n) polymers also comprise a crosslinkingagent, which is most typically a material containing two or moreunsaturated functional groups. The crosslinking agent is reacted withthe monomer units of the polymer and is incorporated into the polymerthereby forming links or covalent bonds between two or more individualpolymer chains or between two or more sections of the same polymerchain. Nonlimiting examples of suitable crosslinking agents includethose selected from the group consisting of methylenebisacrylamides,diallyldialkyl ammonium halides, polyalkenyl polyethers of polyhydricalcohols, allyl acrylates, vinyloxyalkylacrylates, and polyfunctionalvinylidenes. Specific examples of crosslinking agents useful hereininclude those selected from the group consisting ofmethylenebisacrylamide, ethylene glycol di-(meth)acrylate,di-(meth)acrylamide, cyanomethylacrylate, vinyloxyethylacrylate,vinyloxyethylmethacrylate, allyl pentaerythritol, trimethylolpropanediallylether, allyl sucrose, butadiene, isoprene, divinyl benzene,divinyl naphthalene, ethyl vinyl ether, methyl vinyl ether, and allylacrylate. Other crosslinkers include formaldehyde and glyoxal. Preferredfor use herein as a crosslinking agent is methylenebisacrylamide.

Widely varying amounts of the crosslinking agent can be employeddepending upon the properties desired in the final polymer, e.g.viscosifying effect. Without being limited by theory, it is believedthat incorporation of a crosslining agent into these cationic polymersprovides a material that is a more effective viscosifying agent withoutnegatives such as stringiness and viscosity breakdown in the presence ofelectrolytes. The crosslinking agent, when present, can comprise fromabout 1 ppm to about 1000 ppm, preferably from about 5 ppm to about 750ppm, more preferably from about 25 ppm to about 500 ppm, even morepreferably from about 100 ppm to about 500 ppm, and most preferably fromabout 250 ppm to about 500 ppm of the total weight of the polymer on aweight/weight basis.

The intrinsic viscosity of the crosslinked polymer, measured in onemolar sodium chloride solution at 25° C., is generally above 6,preferably from about 8 to about 14. The molecular weight (weightaverage) of the crosslinked polymers hereof is high, and is believed totypically be between about 1 million and about 30 million. The specificmolecular weight is not critical and lower or higher weight averagemolecular weights can be used as long as the polymer retains itsintended viscosifying effects. Preferably, a 1.0% solution of thepolymer (on an actives basis) in deionized water will have a viscosityat 25° C. of at least about 20,000 cP, preferably at least about 30,000cP, when measured at 20 RPM by a Brookfield RVT (Brookfield EngineeringLaboratories, Inc. Stoughton, Mass., USA).

These cationic polymers can be made by polymerization of an aqueoussolution containing from about 20% to about 60%, generally from about25% to about 40%, by weight monomer, in the presence of an initiator(usually redox or thermal) until the polymerization terminates. Thecrosslinking agent can also be added to the solution of the monomers tobe polymerized, to incorporate it into the polymer. In thepolymerization reactions, the temperature generally starts between about0° and 95° C. The polymerization can be conducted by forming a reversephase dispersion of an aqueous phase of the monomers (and also anyadditional crosslinking agents) into a nonaqueous liquid, e.g. mineraloil, lanolin, isododecane, oleyl alcohol, and other volatile andnonvolatile esters, ethers, and alcohols, and the like.

All percentages describing the polymer in this section of thedescription herein are molar, unless otherwise specified. When thepolymer contains (C) monomer, the molar proportion of (C) monomer, basedon the total molar amount of (A), (B), and (C), can be from 0% to about99%. The molar proportions of (A) and (B) can each be from 0% to 100%.When acrylamide, is used as the (C) monomer, it will preferably be usedat a level of from about 20% to about 99%, more preferably from about50% to about 90%.

Where monomer (A) and (B) are both present, the ratio of monomer (A) tomonomer (B) in the final polymer, on a molar basis, is preferably fromabout 99:5 to about 15:85, more preferably from about 80:20 to about20:80. Alternatively, in another class of polymers, the ratio is fromabout 5:95 to about 50:50, preferably from about 5:95 to about 25:75.

In another alternative class of polymers, the ratio (A):(B) is fromabout 50:50 to about 85:15. Preferably the ratio (A):(B) is about 60:40to about 85:15, most preferably about 75:25 to about 85:15.

Most preferred is where monomer (A) is not present and the ratio ofmonomer (B):monomer (C) is from about 30:70 to about 70:30, preferablyfrom about 40:60 to about 60:40 and most preferably from about 45:55 toabout 55:45.

Cationic polymers that are useful herein that are especially preferredare those conforming to the general structure (A)l(B)m(C)n wherein l iszero, (B) is methyl quaternized dimethylaminoethyl methacrylate, theratio of (B):(C) is from about 45:55 to about 55:45, and thecrosslinking agent is methylenebisacrylamide. An example of such acationic polymer is one that is commercially available as a mineral oildispersion (which can also include various dispersing aids such as PPG-1trideceth-6) under the trademark Salcare® SC92 from Allied Colloids Ltd.(Norfolk, Va.). This polymer has the proposed CTFA designation,"Polyquaternium 32 (and) Mineral Oil".

Other cationic polymers useful herein, are those not containingacrylamide or other (C) monomers, that is, n is zero. In these polymersthe (A) and (B) monomer components are as described above. An especiallypreferred group of these non-acrylamide containing polymers is one inwhich 1 is also zero. In this instance the polymer is essentially ahomopolymer of a dialkylaminoalkyl methacrlyate monomer or itsquaternary ammonium or acid addition salt. These diaklylaminoalkylmethacrylate polymers preferably contain a crosslinking agent asdescribed above.

A cationic polymer, which is essentially a homopolymer, useful herein isone conforming to the general structure (A)_(l) (B)_(m) (C)_(n) whereinl is zero, (B) is methyl quaternized dimethylaminoethyl methacrylate, nis zero, and the crosslinking agent is methylenebisacrylamide. Anexample of such a homopolymer is commercially available as a mixturecontaining approximately 50% of the polymer, approximately 44% mineraloil, and approximately 6% PPG-l trideceth-6 as a dispersing aid, fromAllied Colloids Ltd, (Norfolk, Va.) under the trademark Salcare® SC95.This polymer has recently been given the CTFA designation"Polyquaternium 37 (and) Mineral Oil (and) PPG-1 Trideceth-6".

(iii) Polyacrylamide Polymers

Also useful herein are polyacrylamide polymers, especially non-ionicpolyacrylamide polymers including substituted branched or unbranchedpolymers. These polymers can be formed from a variety of monomersincluding acrylamide and methacrylamide which are unsubstituted orsubstituted with one or two alkyl groups (preferably C₁ to C₅).Preferred are acrylate amide and methacrylate amide monomers in whichthe amide nitrogen is unsubstituted, or substituted with one or two C₁to C₅ alkyl groups (preferably methyl, ethyl, or propyl), for example,acrylamide, methacrylamide, N-methacrylamide, N-methylmethacrylamide,N,N-dimethylmethacrylamide, N-isopropylacrylamide,N-isopropylmethacrylamide, and N,N-dimethylacrylamide. These polymershave a molecular weight greater than about 1,000,000 preferably greaterthan about 1,5000,000 and range up to about 30,000,000. Most preferredamong these polyacrylamide polymers is the nonionic polymer given theCTFA designation polyacrylamide and isoparaffin and laureth-7, availableunder the Tradename Sepigel 305 from Seppic Corporation (Fairfield,N.J.).

Other polyacrylamide polymers useful herein include multi-blockcopolymers of acrylamides and substituted acrylamides with acrylic acidsand substituted acrylic acids. Commercially available examples of thesemulti-block copolymers include Hypan SR150H, SSS0OV, SS500W, SSSA100H,from Lipo Chemicals, Inc., (Patterson, N.J.).

(iv) Polysaccharides

A wide variety of polysaccharides are useful herein. By"polysaccharides" are meant gelling agents containing a backbone ofrepeating sugar (i.e. carbohydrate) units. Nonlimiting examples ofpolysaccharide gelling agents include those selected from the groupconsisting of cellulose, carboxymethyl hydroxyethylcellulose, celluloseacetate propionate carboxylate, hydroxyethylcellulose, hydroxyethylethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose,methyl hydroxyethylcellulose, microcrystalline cellulose, sodiumcellulose sulfate, and mixtures thereof. Also useful herein are thealkyl substituted celluloses. In these polymers, the hydroxy groups ofthe cellulose polymer is hydroxyalkylated (preferably hydroxyethylatedor hydroxypropylated) to form a hydroxyalkylated cellulose which is thenfurther modified with a C10-C30 straight chain or branched chain alkylgroup through an ether linkage. Typically these polymers are ethers ofC10-C30 straight or branched chain alcohols with hydroxyalkylcelluloses.Examples of alkyl groups useful herein include those selected from thegroup consisting of stearyl, isostearyl, lauryl, myristyl, cetyl,isocetyl, cocoyl (i.e. alkyl groups derived from the alcohols of coconutoil), palmityl, oleyl, linoleyl, linolenyl, ricinoleyl, behenyl, andmixtures thereof. Preferred among the alkyl hydroxyalkyl celluloseethers is the material given the CTFA designation cetylhydroxyethylcellulose, which is the ether of cetyl alcohol andhydroxyethylcellulose. This material is sold under the tradenameNatrosol® CS Plus from Aqualon Corporation.

Other useful polysaccharides include scleroglucans comprising a linearchain of (1→3) linked glucose units with a (1→6) linked glucose everythree units, a commercially available example of which is Clearogel™ CS11 from Michel Mercier Products Inc. (Mountainside, N.J.).

(v) Gums

Other additional thickening and gelling agents useful herein includematerials which are primarily derived from natural sources. Nonlimitingexamples of these gelling agent gums include materials selected from thegroup consisting of acacia, agar, algin, alginic acid, ammoniumalginate, amylopectin, calcium alginate, calcium carrageenan, carnitine,carrageenan, dextrin, gelatin, gellan gum, guar gum, guarhydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydratedsilica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp,locust bean gum, natto gum, potassium alginate, potassium carrageenan,propylene glycol alginate, sclerotium gum, sodium carboyxmethyl dextran,sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof.

(vi) Crosskinked Vinyl Ether/Maleic Anhydride Copolymers

Other additional thickening and gelling agents useful herein includecrosslinked copolymers of alkyl vinyl ethers and maleic anhydride. Inthese copolymers the vinyl ethers are represented by the formulaR-O-CH═CH₂ wherein R is a C1-C6 alkyl group, preferably R is methyl.Preferred crosslinking agents are C4-C20 dienes, preferably C6 to C16dienes, and most preferably C8 to C12 dienes. A particularly preferredcopolymer is one formed from methyl vinyl ether and maleic anhydridewherein the copolymer has been crosslinked with decadiene, and whereinthe polymer when diluted as a 0.5% aqueous solution at pH 7 at 25° C.has a viscosity of 50,000-70,000 cps when measured using a BrookfieldRTV viscometer, spindle #7 at 10 rpm. This copolymer has the CTFAdesignation PVM/MA decadiene crosspolymer and is commercially availableas Stabileze™ 06 from International Specialty Products (Wayne N.J.).

(vii) Crosskinked poly-(N-vinylpyrrolidones)

Crosslinked polyvinyl(N-pyrrolidones) useful herein as additionalthickening and gelling agents and include those described in U.S. Pat.No. 5,139,770, to Shih et al, issued Aug. 18, 1992, and U.S. Pat. No.5,073,614, to Shih et al., issued Dec. 17, 1991, both patents of whichare incorporated by reference herein in their entirety. These gellingagents typically contain from about 0.25% to about 1% by weight of acrosslinking agent selected from the group consisting of divinyl ethersand dialyl ethers of terminal diols containing from about 2 to about 12carbon atoms, divinyl ethers and diallyl ethers of polyethylene glycolscontaining from about 2 to about 600 units, dienes having from about 6to about 20 carbon atoms, divinyl benzene, vinyl and allyl ethers ofpentaerythritol, and the like. Typically, these gelling agents have aviscosity from about 25,000 cps to about 40,000 cps when measured as a5% aqueous solution at 25° C. using a Brookfield RVT viscometer withSpindle #6 at 10 rpm. Commercially available examples of these polymersinclude ACP-1 120, ACP-1 179, and ACP-1180, available from InternationalSpecialty Products (Wayne, N.J.).

Thickening agents which are suitable for use herein also include thosedisclosed in U.S. Pat. No., 4,387,107, to Klein et al., issued Jun. 7,1983 and "Encyclopedia of Polymer and Thickeners for Cosmetics," R. Y.Lochhead and W. R. Fron, eds., Cosmetics & Toiletries, vol. 108, pp.95-135 (May 1993), which are all incorporated herein by reference intheir entirety.

Preferred compositions of the present invention include a thickeningagent selected from the group consisting of carboxylic acid polymers,crosslinked polyacrylate polymers, polyacrylamide polymers, and mixturesthereof, more preferably selected from the group consisting ofcrosslinked polyacrylate polymers, polyacrylamide polymers, and mixturesthereof.

Optional Components

The topical compositions of the present invention may comprise a widevariety of optional components, provided that such optional componentsare physically and chemically compatible with the essential componentsdescribed herein, and do not unduly impair stability, efficacy or otheruse benefits associated with the compositions of the present invention.Optional components may be dispersed, dissolved or the like in thecarrier of the present compositions.

Optional components include aesthetic agents and active agents. Forexample, the compositions may include, in addition to the essentialcomponents of the invention, absorbents (including oil absorbents suchas clays an polymeric absorbents), abrasives, anticaking agents,antifoaming agents, antimicrobial agents (e.g., a compound capable ofdestroying microbes, preventing the development of microbes orpreventing the pathogenic action of microbes and useful, for example, incontrolling acne and/or preserving the topical composition), binders,biological additives, buffering agents, bulking agents, chemicaladditives, cosmetic biocides, denaturants, cosmetic astringents, drugastringents, external analgesics, film formers, humectants, opacifyingagents, fragrances, perfumes, pigments, colorings, essential oils, skinsensates, emollients, skin soothing agents, skin healing agents, pHadjusters, plasticizers, preservatives, preservative enhancers,propellants, reducing agents, skin-conditioning agents, skin penetrationenhancing agents, skin protectants, solvents, suspending agents,emulsifiers, thickening agents, solubilizing agents, polymers for aidingthe film-forming properties and substantivity of the composition (suchas a copolymer of eicosene and vinyl pyrrolidone, an example of which isavailable from GAF Chemical Corporation as Ganex® V-220), waxes,sunscreens, sunblocks, ultraviolet light absorbers or scattering agents,sunless tanning agents, antioxidants and/or radical scavengers,chelating agents, sequestrants, anti-acne agents, anti-inflammatoryagents, anti-androgens, depilation agents, desquamationagents/exfoliants, organic hydroxy acids, vitamins and derivativesthereof (including water dispersible or soluble vitamins such as VitaminC and ascorbyl phosphates), compounds which stimulate collagenproduction, and natural extracts. Such other materials are known in theart. Nonexclusive examples of such materials are described in Harry'sCosmeticology, 7th Ed., Harry & Wilkinson (Hill Publishers, London1982); in Pharmaceutical Dosage Forms- Disperse Systems; Lieberman,Rieger & Banker, Vols. 1 (1988) & 2 (1989); Marcel Decker, Inc.; in TheChemistry and Manufacture of Cosmetics, 2nd. Ed. deNavarre (Van Nostrand1962-1965); and in The Handbook of Cosmetic Science and Technology 1stEd. Knowlton & Pearce (Elsevier 1993). can also be used in the presentinvention.

In a preferred embodiment, the composition also includes an activeuseful for chronically regulating skin condition. Such materials arethose which manifest skin appearance benefits following chronicapplication of the composition containing such materials. Materialshaving this effect include, but are not limited to, Vitamin B₃ compoundsand retinoids.

Specific examples of optional components include the following.

A. Vitamin B₃ Compounds

In a preferred embodiment, the compositions of the present inventioncomprise a safe and effective amount of a vitamin B₃ compound. Thevitamin B₃ compound enhances the skin appearance benefits of the presentinvention, especially in regulating skin condition, including regulatingsigns of skin aging, more especially wrinkles, lines, and pores. Thecompositions of the present invention preferably comprise from about0.01% to about 50%, more preferably from about 0.1% to about 10%, evenmore preferably from about 0.5% to about 10%, and still more preferablyfrom about 1% to about 5%, most preferably from about 2% to about 5%, ofthe vitamin B3 compound.

As used herein, "vitamin B₃ compound" means a compound having theformula: ##STR3## wherein R is --CONH₂ (i.e., niacinamide), --COOH(i.e., nicotinic acid) or --CH₂ OH (i.e., nicotinyl alcohol);derivatives thereof, and salts of any of the foregoing.

Exemplary derivatives of the foregoing vitamin B₃ compounds includenicotinic acid esters, including non-vasodilating esters of nicotinicacid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylicacids, nicotinic acid N-oxide and niacinamide N-oxide.

Suitable esters of nicotinic acid include nicotinic acid esters of C₁-C₂₂, preferably C₁ -C₁₆, more preferably C₁ -C₆ alcohols. The alcoholsare suitably straight-chain or branched chain, cyclic or acyclic,saturated or unsaturated (including aromatic), and substituted orunsubstituted. The esters are preferably non-vasodilating. As usedherein, "non-vasodilating" means that the ester does not commonly yielda visible flushing response after application to the skin in the subjectcompositions (the majority of the general population would notexperience a visible flushing response, although such compounds maycause vasodilation not visible to the naked eye, i.e., the ester isnon-rubifacient). Non-vasodilating esters of nicotinic acid includetocopherol nicotinate and inositol hexanicotinate; tocopherol nicotinateis preferred.

Other derivatives of the vitamin B₃ compound are derivatives ofniacinamide resulting from substitution of one or more of the amidegroup hydrogens. Nonlimiting examples of derivatives of niacinamideuseful herein include nicotinyl amino acids, derived, for example, fromthe reaction of an activated nicotinic acid compound (e.g., nicotinicacid azide or nicotinyl chloride) with an amino acid, and nicotinylalcohol esters of organic carboxylic acids (e.g., C1-C18). Specificexamples of such derivatives include nicotinuric acid (C₈ H₈ N₂ O₃) andnicotinyl hydroxamic acid (C₆ H₆ N₂ O₂), which have the followingchemical structures: nicotinuric acid: ##STR4## nicotinyl hydroxamicacid: ##STR5##

Exemplary nicotinyl alcohol esters include nicotinyl alcohol esters ofthe carboxylic acids salicylic acid, acetic acid, glycolic acid,palmitic acid and the like. Other non-limiting examples of vitamin B₃compounds useful herein are 2-chloronicotinamide, 6-aminonicotinamide,6-methylnicotinamide, n-methyl-nicotinamide, n,n-diethylnicotinamide,n-(hydroxymethyl)-nicotinamide, quinolinic acid imide, nicotinanilide,n-benzylnicotinamide, n-ethylnicotinamide, nifenazone, nicotinaldehyde,isonicotinic acid, methyl isonicotinic acid, thionicotinamide,nialamide, 1-(3-pyridylmethyl) urea, 2-mercaptonicotinic acid, nicomol,and niaprazine.

Examples of the above vitamin B₃ compounds are well known in the art andare commercially available from a number of sources, e.g., the SigmaChemical Company (St. Louis, Mo.); ICN Biomedicals, Inc. (Irvin, Calif.)and Aldrich Chemical Company milwaukee, Wis.).

One or more vitamin B₃ compounds may be used herein. Preferred vitaminB₃ compounds are niacinamide and tocopherol nicotinate. Niacinamide ismore preferred.

When used, salts, derivatives, and salt derivatives of niacinamide arepreferably those having substantially the same efficacy as niacinamidein the methods of regulating skin condition described herein.

Salts of the vitamin B₃ compound are also useful herein. Nonlimitingexamples of salts of the vitamin B₃ compound useful herein includeorganic or inorganic salts, such as inorganic salts with anionicinorganic species (e.g., chloride, bromide, iodide, carbonate,preferably chloride), and organic carboxylic acid salts (includingmono-, di- and tri- C1-C18 carboxylic acid salts, e.g., acetate,salicylate, glycolate, lactate, malate, citrate, preferablymonocarboxylic acid salts such as acetate). These and other salts of thevitamin B₃ compound can be readily prepared by the skilled artisan, forexample, as described by W. Wenner, "The Reaction of L-Ascorbic andD-Iosascorbic Acid with Nicotinic Acid and Its Amide", J. OrganicChemistry, VOL. 14, 22-26 (1949), which is incorporated herein byreference. Wenner describes the synthesis of the ascorbic acid salt ofniacinamide.

In a preferred embodiment, the ring nitrogen of the vitamin B₃ compoundis substantially chemically free (e.g., unbound and/or unhindered), orafter delivery to the skin becomes substantially chemically free("chemically free" is hereinafter alternatively referred to as"uncomplexed"). More preferably, the vitamin B₃ compound is essentiallyuncomplexed. Therefore, if the composition contains the vitamin B₃compound in a salt or otherwise complexed form, such complex ispreferably substantially reversible, more preferably essentiallyreversible, upon delivery of the composition to the skin. For example,such complex should be substantially reversible at a pH of from about5.0 to about 6.0. Such reversibility can be readily determined by onehaving ordinary skill in the art.

More preferably the vitamin B₃ compound is substantially uncomplexed inthe composition prior to delivery to the skin. Exemplary approaches tominimizing or preventing the formation of undesirable complexes includeomission of materials which form substantially irreversible or othercomplexes with the vitamin B₃ compound, pH adjustment, ionic strengthadjustment, the use of surfactants, and formulating wherein the vitaminB₃ compound and materials which complex therewith are in differentphases. Such approaches are well within the level of ordinary skill inthe art.

Thus, in a preferred embodiment, the vitamin B₃ compound contains alimited amount of the salt form and is more preferably substantiallyfree of salts of a vitamin B₃ compound. Preferably the vitamin B₃compound contains less than about 50% of such salt, and is morepreferably essentially free of the salt form. The vitamin B₃ compound inthe compositions hereof having a pH of from about 4 to about 7 typicallycontain less than about 50% of the salt form.

The vitamin B₃ compound may be included as the substantially purematerial, or as an extract obtained by suitable physical and/or chemicalisolation from natural (e.g., plant) sources. The vitamin B₃ compound ispreferably substantially pure, more preferably essentially pure.

B. Retinoids

In a preferred embodiment, the compositions of the present inventioncontain a retinoid. The retinoid enhances the skin appearance benefitsof the present invention, especially in regulating skin condition,including regulating signs of skin aging, more especially wrinkles,lines, and pores.

As used herein, "retinoid" includes all natural and/or synthetic analogsof Vitamin A or retinol-like compounds which possess the biologicalactivity of Vitamin A in the skin as well as the geometric isomers andstereoisomers of these compounds. The retinoid is preferably retinol,retinol esters (e.g., C₂ -C₂₂ alkyl esters of retinol, including retinylpalmitate, retinyl acetate, retinyl propionate), retinal, and/orretinoic acid (including all-trans retinoic acid and/or 13-cis-retinoicacid), more preferably retinoids other than retinoic acid. Thesecompounds are well known in the art and are commercially available froma number of sources, e.g., Sigma Chemical Company (St. Louis, Mo.), andBoerhinger Mannheim (Indianapolis, Ind.). Other retinoids which areuseful herein are described in U.S. Pat. Nos. 4,677,120, issued Jun. 30,1987 to Parish et al.; 4,885,311, issued Dec. 5, 1989 to Parish et al.;5,049,584, issued Sep. 17, 1991 to Purcell et al.; 5,124,356, issuedJun. 23, 1992 to Purcell et al.; and Reissue 34,075, issued Sep. 22,1992 to Purcell et al.. Other suitable retinoids aretocopheryl-retinoate [tocopherol ester of retinoic acid (trans- orcis-), adapalene {6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoic acid},and tazarotene (ethyl6-[2-(4,4-dimethylthiochroman-6-yl)-ethynyl]nicotinate). One or moreretinoids may be used herein. Preferred retinoids are retinol, retinylpalmitate, retinyl acetate, retinyl proprionate, retinal andcombinations thereof. More preferred are retinol and retinyl palmitate.

The retinoid may be included as the substantially pure material, or asan extract obtained by suitable physical and/or chemical isolation fromnatural (e.g., plant) sources. The retinoid is preferably substantiallypure, more preferably essentially pure.

The compositions of this invention may contain a safe and effectiveamount of the retinoid, such that the resultant composition is safe andeffective for regulating skin condition, preferably for regulatingvisible and/or tactile discontinuities in skin, more preferably forregulating signs of skin aging, even more preferably for regulatingvisible and/or tactile discontinuities in skin texture associated withskin aging. The compositions preferably contain from or about 0.005% toor about 2%, more preferably 0.01% to or about 2%, retinoid. Retinol ismost preferably used in an amount of from or about 0.01% to or about0.15%; retinol esters are most preferably used in an amount of from orabout 0.01% to or about 2% (e.g., about 1%); retinoic acids are mostpreferably used in an amount of from or about 0.01% to or about 0.25%;tocopheryl-retinoate, adapalene, and tazarotene are most preferably usedin an amount of from or about 0.01% to or about 2%.

In a preferred embodiment, the composition contains both a retinoid anda Vitamin B₃ compound. The retinoid is preferably used in the aboveamounts, and the vitamin B₃ compound is preferably used in an amount offrom or about 0.1% to or about 10%, more preferably from or about 2% toor about 5%.

C. Anti-Inflammatory Agents

A safe and effective amount of an anti-inflammatory agent may be addedto the compositions of the subject invention, preferably from about 0.1%to about 10%, more preferably from about 0.5% to about 5%, of thecomposition. The anti-inflammatory agent enhances the skin appearancebenefits of the present invention, e.g., such agents contribute to amore uniform and acceptable skin tone or color. The exact amount ofanti-inflammatory agent to be used in the compositions will depend onthe particular anti-inflammatory agent utilized since such agents varywidely in potency.

Steroidal anti-inflammatory agents, including but not limited to,corticosteroids such as hydrocortisone, hydroxyltriamcinolone,alpha-methyl dexamethasone, dexamethasone-phosphate, beclomethasonedipropionates, clobetasol valerate, desonide, desoxymethasone,desoxycorticosterone acetate, dexamethasone, dichlorisone, diflorasonediacetate, diflucortolone valerate, fluadrenolone, flucloroloneacetonide, fludrocortisone, flumethasone pivalate, fluosinoloneacetonide, fluocinonide, flucortine butylesters, fluocortolone,fluprednidene (fluprednylidene) acetate, flurandrenolone, halcinonide,hydrocortisone acetate, hydrocortisone butyrate, methylprednisolone,triamcinolone acetonide, cortisone, cortodoxone, flucetonide,fludrocortisone, difluorosone diacetate, fluradrenolone,fludrocortisone, diflurosone diacetate, fluradrenolone acetonide,medrysone, amcinafel, amcinafide, betamethasone and the balance of itsesters, chloroprednisone, chlorprednisone acetate, clocortelone,clescinolone, dichlorisone, diflurprednate, flucloronide, flunisolide,fluoromethalone, fluperolone, fluprednisolone, hydrocortisone valerate,hydrocortisone cyclopentylpropionate, hydrocortamate, meprednisone,paramethasone, prednisolone, prednisone, beclomethasone dipropionate,triamcinolone, and mixtures thereof may be used. The preferred steroidalanti-inflammatory for use is hydrocortisone.

A second class of anti-inflammatory agents which is useful in thecompositions includes the nonsteroidal anti-inflammatory agents. Thevariety of compounds encompassed by this group are well-known to thoseskilled in the art. For detailed disclosure of the chemical structure,synthesis, side effects, etc. of non-steroidal anti-inflammatory agents,reference may be had to standard texts, including Anti-inflammatory andAnti-Rheumatic Drugs. K. D. Rainsford, Vol. I-III, CRC Press, BocaRaton, (1985), and Anti-inflammatory Agents, Chemistry and Pharmacology,1, R. A. Scherrer, et al., Academic Press, New York (1974), eachincorporated herein by reference.

Specific non-steroidal anti-inflammatory agents useful in thecomposition invention include, but are not limited to:

1) the oxicams, such as piroxicam, isoxicam, tenoxicam, sudoxicam, andCP-14,304;

2) the salicylates, such as aspirin, disalcid, benorylate, trilisate,safapryn, solprin, diflunisal, and fendosal;

3) the acetic acid derivatives, such as diclofenac, fenclofenac,indomethacin, sulindac, tolmetin, isoxepac, furofenac, tiopinac,zidometacin, acematacin, fentiazac, zomepirac, clindanac, oxepinac,felbinac, and ketorolac;

4) the fenamates, such as mefenamic, meclofenamic, flufenamic, niflumic,and tolfenamic acids;

5) the propionic acid derivatives, such as ibuprofen, naproxen,benoxaprofen, flurbiprofen, ketoprofen, fenoprofen, fenbufen,indopropfen, pirprofen, carprofen, oxaprozin, pranoprofen, miroprofen,tioxaprofen, suprofen, alminoprofen, and tiaprofenic; and

6) the pyrazoles, such as phenylbutazone, oxyphenbutazone, feprazone,azapropazone, and trimethazone.

Mixtures of these non-steroidal anti-inflammatory agents may also beemployed, as well as the dermatologically acceptable salts and esters ofthese agents. For example, etofenamate, a flufenamic acid derivative, isparticularly useful for topical application. Of the nonsteroidalanti-inflammatory agents, ibuprofen, naproxen, flufenamic acid,etofenamate, aspirin, mefenamic acid, meclofenamic acid, piroxicam andfelbinac are preferred; ibuprofen, naproxen, etofenamate, aspirin andflufenamic acid are most preferred.

Finally, so-called "natural" anti-inflammatory agents are useful inmethods of the subject invention. Such agents may suitably be obtainedas an extract by suitable physical and/or chemical isolation fromnatural sources (e.g., plants, fungi, by-products of microorganisms).For example, candelilla wax, alpha bisabolol, aloe vera, Manjistha(extracted from plants in the genus Rubia, particularly RubiaCordifolia), and Guggal (extracted from plants in the genus Commiphoraparticularly Commiphora Mukul), kola extract, chamomile, and sea whipextract, may be used.

Additional anti-inflammatory agents useful herein include compounds ofthe Licorice (the plant genus/species Glycyrrhiza glabra) family,including glycyrrhetic acid, glycyrrhizic acid, and derivatives thereof(e.g., salts and esters). Suitable salts of the foregoing compoundsinclude metal and ammonium salts. Suitable esters include C₂ -C₂₄saturated or unsaturated esters of the acids, preferably C₁₀ -C₂₄, morepreferably C₁₆ -C₂₄. Specific examples of the foregoing include oilsoluble licorice extract the glycyrrhizic and glycyrrhetic acidsthemselves, monoammonium glycyrrhizinate, monopotassium glycyrrhizinate,dipotassium glycyrrhizinate, 1-beta-glycyrrhetic acid, stearylglycyrrhetinate, and 3-stearyloxy-glycyrrhetinic acid, and disodium3-succinyloxy-beta-glycyrrhetinate. Stearyl glycyrrhetinate ispreferred.

D. Sunscreens and Sunblocks

Exposure to ultraviolet light can result in excessive scaling andtexture changes of the stratum corneum. Therefore, the compositions ofthe subject invention preferably contain a sunscreen or sunblock.Suitable sunscreens or sunblocks may be organic or inorganic.

A wide variety of conventional sunscreening agents are suitable for useherein. Sagarin, et al., at Chapter VIII, pages 189 et seq., ofCosmetics Science and Technology (1972) discloses numerous suitableagents, and is incorporated herein by reference. Specific suitablesunscreening agents include, for example: p-aminobenzoic acid, its saltsand its derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); anthranilates (i.e., o-amino-benzoates;methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); salicylates (amyl, phenyl, octyl, benzyl, menthyl,glyceryl, and di-pro-pyleneglycol esters); cinnamic acid derivatives(menthyl and benzyl esters, a-phenyl cinnamonitrile; butyl cinnamoylpyruvate); dihydroxycinnamic acid derivatives (umbelliferone,methylumbelliferone, methylaceto-umbelliferone); trihydroxy-cinnamicacid derivatives (esculetin, methylesculetin, daphnetin, and theglucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene,stilbene); dibenzalacetone and benzalacetophenone; naphtholsulfonates(sodium salts of 2-naphthol-3,6-disulfonic and of2-naphthol-6,8-disulfonic acids); di-hydroxynaphthoic acid and itssalts; o- and p-hydroxybiphenyldisulfonates; coumarin derivatives(7-hydroxy, 7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole,phenyl benzoxazole, methyl naphthoxazole, various aryl benzothiazoles);quinine salts (bisulfate, sulfate, chloride, oleate, and tannate);quinoline derivatives (8-hydroxyquinoline salts, 2-phenylquinoline);hydroxy- or methoxy-substituted benzophenones; uric and violuric acids;tannic acid and its derivatives (e.g., hexaethylether); (butyl carbotol)(6-propyl piperonyl) ether; hydroquinone; benzophenones (oxybenzene,sulisobenzone, dioxybenzone, benzoresorcinol,2,2',4,4'-tetrahydroxybenzophenone,2,2'-dihydroxy-4,4'-dimethoxybenzophenone, octabenzone;4-isopropyldibenzoylmethane; butylmethoxydibenzoylmethane; etocrylene;octocrylene; [3-(4'-methylbenzylidene bornan-2-one) and4-isopropyl-di-benzoylmethane.

Of these, 2-ethylhexyl-p-methoxycinnamate (commercially available asPARSOL MCX), 4,4'-t-butyl methoxydibenzoyl-methane (commerciallyavailable as PARSOL 1789), 2-hydroxy-4-methoxybenzophenone,octyldimethyl-p-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy4-methoxybenzophenone,ethyl-4-(bis(hydroxy-propyl))aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-salicylate,glyceryl-p-aminobenzoate, 3,3,5-tri-methylcyclohexylsalicylate,methylanthranilate, p-dimethyl-aminobenzoic acid or aminobenzoate,2-ethylhexyl-p-dimethyl-amino-benzoate, 2-phenylbenzimidazole-5-sulfonicacid, 2-(p-dimethylaminophenyl)-5-sulfonicbenzoxazoic acid, octocryleneand mixtures of these compounds, are preferred.

More preferred organic sunscreens useful in the compositions useful inthe subject invention are 2-ethylhexyl-p-methoxycinnamate,butylmethoxydibenzoyl-methane, 2-hydroxy4-methoxybenzo-phenone,2-phenylbenzimidazole-5-sulfonic acid, octyldimethyl-p-aminobenzoicacid, octocrylene and mixtures thereof.

Also particularly useful in the compositions are sunscreens such asthose disclosed in U.S. Pat. No. 4,937,370 issued to Sabatelli on Jun.26, 1990, and U.S. Pat. No. 4,999,186 issued to Sabatelli & Spirnak onMar. 12, 1991, both of which are incorporated herein by reference. Thesunscreening agents disclosed therein have, in a single molecule, twodistinct chromophore moieties which exhibit different ultra-violetradiation absorption spectra. One of the chromophore moieties absorbspredominantly in the UVB radiation range and the other absorbs stronglyin the UVA radiation range.

Preferred members of this class of sunscreening agents are4-N,N-(2-ethylhexyl)methyl-aminobenzoic acid ester of2,4-dihydroxybenzophenone; N,N-di-(2-ethylhexyl)-4-aminobenzoic acidester with 4-hydroxydibenzoylmethane;4-N,N-(2-ethylhexyl)methyl-aminobenzoic acid ester with4-hydroxydibenzoylmethane; 4-N,N-(2-ethylhexyl)methyl-aminobenzoic acidester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone;4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane;N,N-di-(2-ethylhexyl)-4-aminobenzoic acid ester of2-hydroxy4-(2-hydroxyethoxy)benzophenone; andN,N-di-(2-ethylhexyl)-4-aminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane and mixtures thereof.

Especially preferred sunscreens or sunblocks includebutylmethoxydibenzoylmethane, 2-ethylhexyl-p-methoxycinnamate, phenylbenzimidazole sulfonic acid, and octocrylene.

A safe and effective amount of the sunscreen or sunblock is used,typically from about 1% to about 20%, more typically from about 2% toabout 10%. Exact amounts will vary depending upon the sunscreen chosenand the desired Sun Protection Factor (SPF).

An agent may also be added to any of the compositions useful in thesubject invention to improve the skin substantivity of thosecompositions, particularly to enhance their resistance to being washedoff by water, or rubbed off. A preferred agent which will provide thisbenefit is a copolymer of ethylene and acrylic acid. Compositionscomprising this copolymer are disclosed in U.S. Pat. No. 4,663,157,Brock, issued May 5, 1987, which is incorporated herein by reference.

E. Anti-Oxidants/Radical Scavengers

Preferred compositions of the subject invention include ananti-oxidant/radical scavenger. The anti-oxidant/radical scavenger isespecially useful for providing protection against UV radiation whichcan cause increased scaling or texture changes in the stratum corneumand against other environmental agents which can cause skin damage.

A safe and effective amount of an anti-oxidant/radical scavenger may beadded to the compositions of the subject invention, preferably fromabout 0.1% to about 10%, more preferably from about 1% to about 5%, ofthe composition.

Anti-oxidants/radical scavengers such as ascorbic acid (vitamin C) andits salts, ascorbyl esters of fatty acids, ascorbic acid derivatives(e.g., magnesium ascorbyl phosphate), tocopherol (vitamin E), tocopherolsorbate, tocopherol acetate, other esters of tocopherol, butylatedhydroxy benzoic acids and their salts,6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (commerciallyavailable under the tradename Trolox®), gallic acid and its alkylesters, especially propyl gallate, uric acid and its salts and alkylesters, sorbic acid and its salts, amines (e.g.,N,N-diethylhydroxylamine, amino-guanidine), sulfhydryl compounds (e.g.,glutathione), dihydroxy fumaric acid and its salts, lycine pidolate,arginine pilolate, nordihydroguaiaretic acid, bioflavonoids, lysine,methionine, proline, superoxide dismutase, silymarin, tea extracts,grape skin/seed extracts, melanin, and rosemary extracts may be used.Preferred anti-oxidants/radical scavengers are selected from tocopherolsorbate and other esters of tocopherol, more preferably tocopherolsorbate. For example, the use of tocopherol sorbate in topicalcompositions and applicable to the present invention is described inU.S. Pat. No. 4,847,071, issued on Jul. 11, 1989 to Donald L. Bissett,Rodney D. Bush and Ranjit Chatterjee, incorporated herein by reference.

F. Chelators

As used herein, "chelating agent" means an active agent capable ofremoving a metal ion from a system by forming a complex so that themetal ion cannot readily participate in or catalyze chemical reactions.The inclusion of a chelating agent is especially useful for providingprotection against UV radiation which can contribute to excessivescaling or skin texture changes and against other environmental agentswhich can cause skin damage.

A safe and effective amount of a chelating agent may be added to thecompositions of the subject invention, preferably from about 0.1% toabout 10%, more preferably from about 1% to about 5%, of thecomposition. Exemplary chelators that are useful herein are disclosed inU.S. Pat. No. 5,487,884, issued Jan. 30, 1996 to Bissett et al.;International Publication No. 91/16035, Bush et al., published Oct. 31,1995; and International Publication No. 91/16034, Bush et al., publishedOct. 31, 1995; all incorporated herein by reference. Preferred chelatorsuseful in compositions of the subject invention are furildioxime andderivatives thereof.

G. Organic Hydroxv Acids

Compositions of the present invention may comprise an organic hydroxyacid. Suitable hydroxy acids include C₁ -C₁₈ hydroxy acids, preferablyC₈ or below. The hydroxy acids can be substituted or unsubstituted,straight chain, branched chain or cyclic (preferably straight chain),and saturated or unsaturated (mono- or poly-unsaturated) (preferablysaturated). Non-limiting examples of suitable hydroxy acids includesalicylic acid, glycolic acid, lactic acid, 5 octanoyl salicylic acid,hydroxyoctanoic acid, hydroxycaprylic acid, and lanolin fatty acids.Preferred concentrations of the organic hydroxy acid range from about0.1% to about 10%, more preferably from about 0.2% to about 5%, alsopreferably from about 0.5% to about 2%. Salicylic acid is preferred. Theorganic hydroxy acids enhance the skin appearance benefits of thepresent invention. For example, the organic hydroxy acids tend toimprove the texture of the skin.

H. Desquamation Agents/Exfoliants

A safe and effective amount of a desquamation agent may be added to thecompositions of the subject invention, more preferably from about 0.1%to about 10%, even more preferably from about 0.2% to about 5%, alsopreferably from about 0.5% to about 4% of the composition. Desquamationagents enhance the skin appearance benefits of the present invention.For example, the desquamation agents tend to improve the texture of theskin (e.g., smoothness). A variety of desquamation agents are known inthe art and are suitable for use herein, including but not limited tothe organic hydroxy agents described above. One desquamation system thatis suitable for use herein comprises sulfihydryl compounds andzwitterionic surfactants and is described in copending application Ser.No. 08/480,632, filed on Jun. 7, 1995 in the name of Donald L. Bissett,corresponding to PCT Application No. U.S. 95/08136, filed Jun. 29, 1995,each incorporated herein by reference. Another desquamation system thatis suitable for use herein comprises salicylic acid and zwitterionicsurfactants and is described in copending patent application Ser. No.08/554,944, filed on Nov. 13, 1995 as a continuation of Ser. No.08/209,401, filed on Mar. 9, 1994 in the name of Bissett, correspondingto PCT Application No. 94/12745, filed 11/4/94, published May 18, 1995,each incorporated herein by reference. Zwitterionic surfactants such asdescribed in these applications are also useful as desquamatory agentsherein, with cetyl betaine being particularly preferred.

I. Skin Lightening Agents

The compositions of the present invention may comprise a skin lighteningagent. When used, the compositions preferably comprise from about 0.1%to about 10%, more preferably from about 0.2% to about 5%, alsopreferably from about 0.5% to about 2%, of a skin lightening agent.Suitable skin lightening agents include those known in the art,including kojic acid, arbutin, ascorbic acid and derivatives thereof,e.g., magnesium ascorbyl phosphate. Skin lightening agents suitable foruse herein also include those described in copending patent applicationSer. No. 08/479,935, filed on Jun. 7, 1995 in the name of Hillebrand,corresponding to PCT Application No. U.S. 95/07432, filed Jun. 12, 1995;and copending patent application Ser. No. 08/390,152, fled on Feb. 24,1995 in the names of Kalla L. Kvalnes, Mitchell A. DeLong, Barton J.Bradbury, Curtis B. Motley, and John D. Carter, corresponding to PCTApplication No. U.S. 95/02809, filed Mar. 1, 1995, published Sep. 8,1995; all incorporated herein by reference.

J. Skin Conditioners

Preferred compositions of the invention comprise an optional skinconditioning component comprising one or more skin conditioningcompounds. The skin conditioning component is useful for lubricating theskin, increasing the smoothness and suppleness of the skin, preventingor relieving dryness of the skin, hydrating the skin, and/or protectingthe skin. The skin conditioning component enhances the skin appearanceimprovements of the present invention, including but not limited toessentially immediate visual improvements in skin appearance. The skinconditioning component is preferably selected from the group consistingof emollients, humectants, moisturizers and mixtures thereof. The skinconditioning component is preferably present at a level of at leastabout 0.1%, more preferably from about 1% to about 99%, even morepreferably from about 1% to about 50%, still more preferably from about2% to about 30% and most preferably from about 5% to about 25% (e.g.,about 5% to about 10% or 15%). Compositions containing the skinconditioning component tend to have the preferred Hydration Factorsdescribed herein.

A variety of emollients may be employed. These emollients may beselected from one or more of the following classes: Triglyceride esterswhich include, but are not limited to, vegetable and animal fats andoils such as castor oil, cocoa butter, safflower oil, cottonseed oil,corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil,sesame oil, squalene, kikui oil and soybean oil; Acetoglyceride esters,such as acetylated monoglycerides; Ethoxylated glycerides, such asethoxylated glyceryl monostearate; Alkyl esters of fatty acids having 10to 20 carbon atoms which include, but are not limited to, methyl,isopropyl, and butyl esters of fatty acids such as hexyl laurate,isohexyl laurate, isohexyl palmitate, isopropyl palmitate, methylpalmitate, decyloleate, isodecyl oleate, hexadecyl stearate decylstearate, isopropyl isostearate, methyl isostearate, diisopropyladipate, diisohexyl adipate, dihexyldecyl adipate, diisopropyl sebacate,lauryl lactate, myristyl lactate, and cetyl lactate; Alkenyl esters offatty acids having 10 to 20 carbon atoms such as oleyl myristate, oleylstearate, and oleyl oleate; Fatty acids having 10 to 20 carbon atomssuch as pelargonic, lauric, myristic, palmitic, stearic, isostearic,hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic, anderucic acids; Fatty alcohols having 10 to 20 carbon atoms such aslauryl, myristyl, cetyl, hexadecyl, stearyl, isostearyl, hydroxystearyl,oleyl, ricinoleyl, behenyl, erucyl, and 2-octyl dodecanyl alcohols;Lanolin and lanolin derivatives such as lanolin, lanolin oil, lanolinwax, lanolin alcohols, lanolin fatty acids, isopropyl lanolate,ethoxylated cholesterol, propoxylated lanolin alcohols, acetylatedlanolin alcohols, lanolin alcohols linoleate, lanolin alcoholsricinoleate, acetate of lanolin alcohols ricinoleate, acetate ofethoxylated alcohols-esters, hydrogenolysis of lanolin, ethoxylatedhydrogenated lanolin, and liquid and semisolid lanolin absorption bases;Polyhydric alcohol esters such as ethylene glycol mono and di-fatty acidesters, diethylene glycol mono-and di-fatty acid esters, polyethyleneglycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono-and di-fatty acid esters, polypropylene glycol 2000 monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpolyfatty esters, ethoxylated glyceryl monostearate, 1,2-butylene glycolmonostearate, 1,2-butylene glycol distearate, sorbitan fatty acidesters, and polyoxyethylene sorbitan fatty acid esters; Wax esters suchas beeswax, spermaceti, myristyl myristate, stearyl stearate; Beeswaxderivatives such as polyoxyethylene sorbitol beeswax which are reactionproducts of beeswax with ethoxylated sorbitol of varying ethylene oxidecontent, forming a mixture of ether esters; Vegetable waxes including,but not limited to, carnauba and candelilla waxes; Phospholipids such aslecithin and derivatives; Sterols including, but not limited to,cholesterol and cholesterol fatty acid esters; and Amides such as fattyacid amides, ethoxylated fatty acid amides, and solid fatty acidalkanolamides.

Additional types of conditioning compounds are humectants of thepolyhydric alcohol-type. Typical polyhydric alcohols includepolyalkylene glycols and more preferably alkylene polyols and theirderivatives, including propylene glycol, dipropylene glycol,polypropylene glycol, polyethylene glycol and derivatives thereof,sorbitol, hydroxypropyl sorbitol, erythritol, threitol, pentaerythritol,xylitol, glucitol, mannitol, hexylene glycol, butylene glycol (e.g.,1,3-butylene glycol), hexane triol (e.g., 1,2,6-hexanetriol), glycerol,ethoxylated glycerol, propoxylated glycerol, sodium2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl phthalate,gelatin and mixtures thereof.

Also useful herein are guanidine; glycolic acid and glycolate salts(e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactatesalts (e.g. ammonium and quaternary alkyl ammonium); aloe vera in any ofits variety of forms (e.g., aloe vera gel); sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid and derivatives thereof(e.g., salt derivatives such as sodium hyaluraonate); lactamidemonoethanolamine; acetamide monoethanolamine; urea; panthenol; sugars;starches; silicone fluids; silicone gums; and mixtures thereof. Alsouseful are the propoxylated glycerols described in U.S. Pat. No.4,976,953, which is description is incorporated herein by reference.Other useful conditioning compounds include the various C₁ -C₃₀monoesters and polyesters of sugars and related materials such asdescribed herein in reference to the hydrophobic component.

The above listed compounds may be incorporated singly or in combination.

Preparation of Compositions

The compositions of the present invention are generally prepared byconventional methods such as are known in the art of making topicalcompositions. Such methods typically involve mixing of the ingredientsin one or more steps to a relatively uniform state, with or withoutheating, cooling, application of vacuum, and the like.

Properties of the compositions

The compositions of the present invention are characterized by theirContrast Ratio and % Transmittance or Coverage Index. The compositionsmay be further characterized by their Apparent Viscosity and/orHydration Factor.

a) Contrast Ratio

Compositions of the present invention have a contrast ratio of fromabout 9 to about 30, more preferably from about 11 to about 22. Contrastratio can be determined by the following Contrast Ratio Method, using anopacity chart (form 2A, Leneta Company of Manwah, N.J. or the equivalentthereof), and a chromameter (e.g., a Minolta CR-200 Chromameter, d65illuminant, 0 degree viewing angle, equipped with a specular component,commercially available from the Minolta Camera Co. of Ramsey, N.J. anddescribed in the chromameter manual, version 3.0; 1988, incorporatedherein by reference, or the equivalent thereof).

The opacity chart is half black (top) and half white (bottom), with thecolors being separated along a line parallel to the horizon. 4 grams ofa test product are applied in about a 1/2"×3" area at the top of theopacity chart. The product is drawn down the length of the card, throughboth halves and generally symmetrically, into a thin film using a 1.5mil film applicator (e.g., as commercially available from BYK Gardner ofColumbia, Md., or the equivalent thereof. The film is allowed to dry for24 hours under conditions of 25° C. ±1° C., 1 atm.

Using the chromameter, the Y tristimulus value (i.e., the XYZ colorspace of the film) of the product film is measured and recorded. The Ytristimulus value is measured in three different areas of the productfilm over the black section of the opacity chart, and also in threedifferent areas of the product film over the white section of theopacity chart. Areas which are measured are those having an evendistribution of product over the area.

The contrast ratio is calculated as the mathematical average of thethree Y tristimulus values over the black areas, divided by themathematical average of the three Y tristimulus values over the whiteareas, times 100: ##EQU1##

b) % Transmittance and Coverage Index

Compositions of the present invention have a % transmittance of about92% to about 62%, more preferably from about 85% to about 75%, and acoverage index of from about 6 to about 30, more preferably from about10 to about 20. Coverage index and % transmittance can be determined bythe following Coverage Method.

The determination of % transmission and coverage index involvesmeasuring the transmission of light through a collagen film to whichproduct has been applied, relative to a control film. The methodologyrequires a light source sufficiently powerful for sample illumination, acamera and video frame grabber for capturing the image of the sample onthe collagen surface and a computer with video imaging software for dataanalysis and for viewing on a video monitor. Suitable image capture andanalysis software includes Optimas 5.2 from Optimas Corp., Washington(refer to Image Analysis Software guide Volume I), the software andguide being incorporated herein by reference.

Using a collagen film (such as IMS #1192 or equivalent available fromIMS Inc. Milford Conn.) mounted in a suitable holder, apply 40microliters (using a Microman M50 pipette) of product and spread evenlyby hand on the film surface using 10 finger rotations. Optionally, thesample is mounted on a Zeiss SV-11 microscope (or equivalent) equippedwith a 1X lens (the microscope is useful for enlarging the image whichthe camera is capturing; the effective magnification of this system isabout 5 microns/pixel). A mounting template can optionally be employedto aid in repositioning the sample for multiple measurements. The SV-11should be set up so that maximum light is being transmitted to thecamera (e.g., a Sony 760-MD CCD 3 Camera). To insure proper positioningand a clear image, the equipment is set in the following manner. Cameracontrols are set so that the Gamma and Linear matrix switches are off.The camera control box settings are further defined as follows: Gain=0,White/Black balance on auto, iris- auto, mode-camera, detail-12 o'clockposition, phase-0 degrees, SC-3 o'clock position, H-12 o'clock position,Color temp - 3200K, shutter off. The camera should be allowed to warm upfor 15 minutes before adjusting white and black balance. Press thebutton labeled "white" to adjust the white balance, and adjust blackbalance by pulling the black adjustment rod and pushing the button thatsays black. Computer cables are connected to the RGB1 and CompositeSync.ports on the camera. The microscope Iris is set to completely openand a frosted glass plate is positioned in the microscope base for auniformly lit field. A clear glass plate may optionally be used toadjust the sample height. Open the Optimas 5.2 program on the computer.Use a sample cup which is partially covered with black tape in the lightpath to adjust gain and offset (brightness). The reflecting mirror atthe base of the microscope is set for maximum reflection into themicroscope. The mean of the light source should be 245 to 254.5. The STDDeviation should be less than 3. If the mean is out of specificationscheck the light bulb alignment and mirror adjustment.

For the control, an untreated piece of collagen firm (such as IMS #1192available from IMS Inc. Milford Conn.), is mounted on a sample cup whichis placed on the microscope such that the film lies in the center of thelight path. The film is focused and light transmission through the filmis measured using the image capture and analysis software. Multiplemeasurements are taken from separate areas of the sample, repositioningand refocusing the film for each measurement (seven or more measurementsare taken). The histogram mean and standard deviation are determinedusing the image capture and analysis software.

For measuring light transmission by the test product, a piece ofcollagen film is first pre-hydrated with distilled water to insureflexibility. 40 microliters of test product is then dispensed on thefilm (e.g., using a Microman M50 pipette or equivalent), and spreadevenly over its surface to produce an even film covering the surface ofthe collagen (generally by lightly spreading the material by applying 10rotations of the finger, wearing a clean, latex finger cot, to thematerial). After waiting for a period of 5 minutes, the sample ismounted on the microscope base. Light transmission measurements throughthe film and product are then taken in the manner described for thecontrol.

Least significant differences can be performed on the data usingFischer's LSD method.

The coverage index and % transmission are calculated as follows:

    Coverage Index=Control Mean-Test Product Mean/Control Mean×100

    %Transmission=100-Coverage Index

c) Apparent Viscosity

Preferred compositions have an apparent viscosity of from about 5,000 toabout 200,000 centipoise (cps), for example, from about 20,000 to about150,000 cps, from about 25,000 to about 100,000 cps, or from about40,000 to about 70,000 cps (e.g, about 60,000 cps). Nonlimitingexemplary lotions have an apparent viscosity of from about 10,000 toabout 40,000 cps; nonlimiting exemplary creams have an apparentviscosity of from about 60,000 to about 160,000 cps. Apparent viscositycan be determined using a Brookfield DVII RV viscometer, spindle TD, at5rpm, or the equivalent thereof. The viscosity is determined on thecomposition after the composition has been allowed to stabilizefollowing its preparation, generally at least 24 hours under conditionsof 25° C. ±1° C. and ambient pressure after preparation of thecomposition. Apparent viscosity is measured with the composition at atemperature of 25° C.±1° C., after 30 seconds spindle rotation.

d) Hydration Factor

Preferred compositions of the present invention have a Hydration Factorof at least zero as measured by the Skin Moisturizer Hydration Test. TheSkin Moisturizer Hydration Test evaluates and compares the in-vivo,hydration efficacy of topical compositions. The test method utilizes aCourage and Khazaka Comeometer 820 PC to measure the electricalcapacitance of the skin surface. Without being limited by theory, it isbelieved that the electrical capacitance is an indirect measurement ofwater presence and therefore skin surface hydration.

The Skin Moisturizer Hydration Test is determined using at least 16subjects in general good health (free of medical conditions, adversereactions or sensitivities which might affect the skin test results). Ingeneral, the products to be tested are applied to the forearms of eachsubject, in an area not having excessive amounts of hair, dermatitis orscars. More specifically, at least two, 3×4 cm², test regions areidentified on the volar region of the same forearm. The composition ofthe present invention is applied to one test region (3 μl/cm²) and areference (or control) composition is applied to the other test region(3 μl/cm²).

An oil-in-water emulsion providing a specific level of hydration andhaving the following formulation is used as the reference composition:

    ______________________________________                                        Ingredient (CTFA Name as applicable)                                                                      Weight %                                          ______________________________________                                        PHASE A:                                                                              Water U.S.P.            78.96                                            Disodium EDTA 0.15                                                            Glycerin 5                                                                   PHASE B: Cetyl hydroxy ethyl cellulose 0.15                                    Methyl Paraben 0.25                                                          PHASE C: Cetyl Alcohol 0.5                                                     Stearyl Alcohol 0.5                                                           Behenyl Alcohol 0.5                                                           Cetyl ricinoleate 3                                                           Steareth-2 (Brij 72) 1.05                                                     Distearyldimonium chloride (Varisoft TA-100) 0.25                             Propyl Paraben 0.10                                                           Myristyl myristate 1.5                                                        Caprylic/Capritryglycerides 1.5                                               Mineral oil 2                                                                 Fatty acid ester of sugar* 1                                                  Polypropylene glycol-15 stearyl ether 1.05                                    (Arlamol E)                                                                  PHASE D: dimethicone 10 cst (Dow Corning) 2                                   PHASE E: Benzyl Alcohol 0.5                                                   PHASE F: 50% NaOH 0.04                                                      ______________________________________                                         *A C1-C30 monoester of polyester of sugars and one or more carboxylic aci     moieties as described                                                    

Blend the A phase components with a suitable mixer (e.g., Tekmar modelRW2ODZ2), heating while stirring to a temperature of about 70-80° C. Addthe cetyl hyroxy ethyl cellulose and methyl paraben with mixing at about70-80° C. to melt the components. Separately, blend the C phasecomponents and mill to obtain an acceptably smooth mixture (e.g., usinga Tekmar T50 Mill). Add the C phase mixture to the above mixture andmix. Remove the combination from the bath, with continued stirring, oncethe temperature reaches about 45° C. Add the dimethicone and mix. Addand mix in the benzyl alcohol, then the NaOH. Adjust the pH as necessaryto 7.

Test Method: Apply the composition to the subject's skin as describedabove. Spread the composition on the test region by rubbing in acircular motion, using a cotted finger until the product has blendedinto the skin completely. Take electrical capacitance values with thecorneometer at baseline (before product application) and then 3 hours,and 6 hours after product application. The corneometer probe should bewiped clean before each test site reading using a non-linting materialsuch as a Kimwipe and zeroed against a dry clean surface to test theintegrity of the system.

For each subject, hydration measurements on treated sites will bebaseline subtracted (the resulting values being referred to as"measurement unit"). A multi-factor analysis of variance using Fischer'sleast significant difference analysis should be applied to compare databetween products.

A comparatively higher corneometer reading indicates higher skin surfacecapacitance and therefore higher skin surface water content orhydration. The difference between the corneometer values of referencecomposition and the test formulation (which have been baseline adjusted)is the Hydration Factor and is illustrated by the following formula:

    Hydration Factor=("Measurement Unit".sub.test formulation)-("Measurement Unit".sub.reference formulation)

Preferred compositions of the present invention have a Hydration Factorof greater than about 0, preferably about 1.5 or more, more preferablyabout 2 or more.

Methods for Regulating Skin Condition

The compositions of the present invention are useful for regulatingmammalian skin condition (especially human skin, more especially humanfacial skin), including regulating visible and/or tactilediscontinuities in skin, e.g., visible and/or tactile discontinuities inskin texture, more especially discontinuities associated with skinaging.

A wide range of quantities of the compositions of the present inventioncan be employed to provide a skin appearance and/or feel benefit.Quantities of the present compositions which are typically applied perapplication are, in mg composition/cm² skin, from about 0.1 mg/cm² toabout 10 mg/cm². A particularly useful application amount is about 2mg/cm². Typically applications would be on the order of about once perday, however application rates can vary from about once per week up toabout three times per day or more.

The compositions of this invention provide a visible improvement in skincondition essentially immediately following application of thecomposition to the skin. Such immediate improvement involves coverage ormasking of skin imperfections such as textural discontinuities(including those associated with skin aging, such as enlarged pores),and/or providing a more even skin tone or color.

In a preferred embodiment, the composition includes an active whichchronically regulates skin condition and is topically appliedchronically. "Chronic topical application" and the like involvescontinued topical application of the composition over an extended periodduring the subject's lifetime, preferably for a period of at least aboutone week, more preferably for a period of at least about one month, evenmore preferably for at least about three months, even more preferablyfor at least about six months, and more preferably still for at leastabout one year. Chronic regulation of skin condition involvesimprovement of skin condition following multiple topical applications ofthe composition to the skin. While benefits are obtainable after variousmaximum periods of use (e.g., five, ten or twenty years), it ispreferred that chronic application continue throughout the subject'slifetime. Typically applications would be on the order of about once perday over such extended periods, however application rates can vary fromabout once per week up to about three times per day or more. Regulatingskin condition involves topically applying to the skin a safe andeffective amount of a composition of the present invention. The amountof the composition which is applied, the frequency of application andthe period of use will vary widely depending upon the active levels of agiven composition and the level of regulation desired, e.g., in light ofthe level of skin aging present in the subject and the rate of furtherskin aging.

Regulating skin condition is preferably practiced by applying acomposition in the form of a skin lotion, cream, cosmetic, or the likewhich is intended to be left on 5 the skin for an extended period, forsome esthetic, prophylactic, therapeutic or other benefit (i.e., a"leave-on" composition). As used herein, "leave-on" compositions excluderinse-off skin cleansing products. After applying the composition to theskin, the leave-on composition is preferably left on the skin for aperiod of at least about 15 minutes, more preferably at least about 30minutes, even more preferably at least about 1 hour, most preferably forat least several hours, e.g., up to about 12 hours.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.Where applicable, ingredients are given in CTFA name.

Examples 1-3

Oil-in-water emulsions are prepared from the following ingredients usingconventional formulating techniques.

    ______________________________________                                                     Ex 1    Ex 2      Ex 3                                           ______________________________________                                        Phase A                                                                             distilled water                                                                            qs 100    qs 100  qs 100                                     Phase B Glycerin 5 5 5                                                         TiO.sub.2 0.75 0.75 0 75                                                     Phase C glycerin 1 1 1                                                         EDTA 0.1 0.1 0.1                                                              Carbopol 954 0.68 0.5 0.5                                                     Carbopol 1382 0.1 0.1 0.1                                                    Phase D Cetyl Alcohol 0.72 0.72 0.72                                           Stearyl Alcohol 0.48 0.48 0.48                                                Stearic Acid 0.1 0.1 0.1                                                      PEG-100 Stearate 0.1 0.1 0.1                                                  Arlatone 2121 1 1 1                                                           Silicone Q21403 2 2 2                                                         Fatty acid ester of 0.67 0.67 0.67                                            sugar.sup.1                                                                   Tocopherol Acetate 0 0 0.5                                                    Niacinamide 2 2 2                                                            Phase E distilled water 2 2 2                                                  NaOH to neutralize to neutralize to neutralize                                 Carbopols Carbopols Carbopols                                               Phase F Urea 2 0 0                                                             D-Panthenol 0 0 0.5                                                           distilled water 5 5 5                                                        Phase G Glydant Plus 0.1 0.1 0.1                                               Glycerin 1 1 1                                                                distilled water 1 1 1                                                        Phase H Methyl Isostearate 1.33 0 0                                            Isopropyl Isostearate 0 1.33 1.33                                             Retinol 0 0 0.04                                                              BHT 0 0 0.05                                                                  Tween 20 0 0 0.04                                                          ______________________________________                                         .sup.1 A Cl-C30 monoester or polyester of sugars and one or more              carboxylic acid moieties as described herein, preferably a sucrose            polyester in which the degree of esterification is 7-8, and in which the      fatty acid moieties are C18 mono and/or diunsaturated and behenic, in a       molar ratio of unsaturates:behenic of 1:7 to 3:5, more preferably the         octaester of sucrose in which there are about 7 behenic fatty acid            moieties and about 1 oleic acid moiety in the molecule, e.g.,  #sucrose       ester of cottonseed oil fatty acids, e.g., SEFA Cottonate.               

First, sparge Phase A ingredients using nitrogen for approximately 15minutes. Phase B ingredients are milled until the TiO₂ is homogeneouslydispersed, and then added to Phase A. Phase C ingredients are thendispersed into Phase A/B until uniform using propeller type mixing andheated the mixture to about 75° C. In a separate vessel, Phase Dingredients are combined and heated to about 75° C. The mixture ofphases A/B/C are then blanketed with a slow, steady stream of nitrogen.Next the Phase D ingredients are homogenized into the mixture of phasesA/B/C using any rotor/stator type of homogenizer for approximately 15minutes. After the 15 minutes, the mixing is switched to low rpm sweepmixing. Next, phase E ingredients are combined and added to the mixtureof phases A-D. Once phase E is mixed and the batch mixture ishomogeneous, the entire batch mixture is cooled. When the batch iscooled to about 50° C., phase F ingredients are added and homogenized.When the batch is cooled to about 40° C., phase G ingredients are addedto the batch mixture. Lastly, when the batch mixture is cooled to about30° C., the phase H ingredients are combined to the batch mixture.Mixing is continued until the batch mixture is uniform.

Apply the composition to a subjects facial skin at the rate of 2 mgcomposition/cm² skin to provide an essentially immediate visualimprovement in skin appearance, e.g., reduced visibility of pores and amore even sldn tone. Apply the composition to a subject's face at thesame rate once or twice daily for a period of 3-6 months, to improveskin surface texture, including diminishing fine lines and wrinkles, inaddition to the essentially immediate improvements in appearance.

Examples 4-5

Oil-in-water emulsions are prepared from the following ingredients usingconventional formulating techniques.

    ______________________________________                                                           Ex 4    Ex 5                                               ______________________________________                                        Phase A  distilled water qs 100    qs 100                                       Phase B Glycerin 6 6                                                           TiO.sub.2 0.75 0.75                                                          Phase C Glycerin 3 3                                                           Carbopol 954 0.4 0.4                                                          EDTA 0.1 0.1                                                                 Phase D Cetyl Palmitate 1.5 1.5                                                Cetyl Alcohol 2.25 2.25                                                       Stearyl Alcohol 1.5 1.5                                                       Stearic Acid 0.31 0.31                                                        PEG-100 Stearate 0.31 0.31                                                    Silicone Wax DC2501 2 2                                                       DC 3225C 1.88 1.88                                                            Dimethicone 200/350cst 0.63 0.63                                              Tocopherol Acetate 0 0.5                                                      Niacinamide 2 2                                                              Phase E distilled water 2 2                                                    NaOH to to                                                                     neutralize neutralize                                                         Carbopol Carbopol                                                           Phase F D-Panthenol 0 0.5                                                      distilled water 0 5                                                          Phase G Glydant PIus 0.1 0.1                                                   distilled water 1 1                                                           glycerin 1 1                                                                 Phase H Isopropyl Palmitate 1.25 1.25                                          Retinol 0 0.04                                                                Tween 80 0 0.04                                                               BHT 0 0.05                                                                 ______________________________________                                    

Prepare in the manner described for Examples 1-3.

Apply the composition to a subject's facial skin at the rate of 2 mgcomposition/cm² skln to provide an essentially immediate visualimprovement in skin appearance, e.g., reduced visibility of pores and amore even skin tone. Apply the composition to a subject's face at thesame rate once or twice daily for a period of 3-6 months, to improveskin surface texture, including diminishing fine lines and wrinkles, inaddition to the essentially immediate improvements in appearance.

While particular embodiments of the subject invention have beendescribed, it will be obvious to those skilled in the art that variouschanges and modifications to the subject invention can be made withoutdeparting from the spirit and scope of the invention. It is intended tocover, in the appended claims, all such modifications that are withinthe scope of the subject invention.

What is claimed:
 1. A topical composition formed by combining componentscomprising:(a) from about 0.3% to about 2% by weight of the compositionformed of pigmentary grade particulate material having a refractiveindex of at least about 2 and a neat primary particle size of fromgreater than 100 nm to about 300 nm; and (b) a topical carriercomprising from about 60% to about 99.7% by weight of the compositionformed of a substantially liquid diluent;the composition having acontrast ratio of from about 9 to about 30 and a % transmittance of fromabout 92% to about 62%.
 2. The composition of claim 1 wherein thecontrast ratio is from about 11 to about 22 and the % transmittance isfrom about 85% to about 75%.
 3. The composition of claim 1 wherein theparticulate material has a refractive index of from about 2 to about 3.4. The composition of claim 1 wherein the particulate material comprisesa material selected from the group consisting of TiO₂, ZnO, ZrO₂, andcombinations thereof.
 5. The composition of claim 1 wherein the totalamount of all particulate material in the composition, by weight % ofthe composition, is about 10% or less.
 6. The composition of claim 1wherein the total amount of all particulate material in the composition,by weight % of the composition, is about 5% or less.
 7. The compositionof claim 1 wherein the total amount of all particulate material in thecomposition, by weight % of the composition, is about 3% or less.
 8. Thecomposition of claim 4 wherein the particulate material consistsessentially of TiO₂.
 9. The composition of claim 1 wherein theparticulate material has a primary particle size when dispersed in thecomposition of from greater than 100 nm to about 1000 nm.
 10. Thecomposition of claim 1 having an apparent viscosity, in centipoise, offrom about 5,000 to about 200,000.
 11. The composition of claim 1 havingan apparent viscosity, in centipoise, of from about 20,000 to about150,000.
 12. The composition of claim 1 having an apparent viscosity, incentipoise, of from about 25,000 to about 100,000.
 13. The compositionof claim 1 further comprising a skin conditioning component.
 14. Thecomposition of claim 1 further having a Hydration Factor of at leastabout
 0. 15. A topical composition formed by combining componentscomprising:(a) from about 0.3% to about 2% by weight of the compositionformed of a pigmentary grade particulate material selected from thegroup consisting of TiO₂, ZnO, ZrO₂, and combinations thereof, andhaving a neat primary particle size of from greater than 100 nm to about300 nm; and (b) a topical carrier comprising from about 60% to about99.7% by weight of the composition formed of a substantially liquiddiluent;wherein the particulate material has a primary particle sizewhen dispersed in the composition of from greater than 100 nm to about1000 nm and the composition has a contrast ratio of from about 9 toabout 30, a % transmittance of from about 92% to about 62%, and anapparent viscosity, in centipoise, of from about 5,000 to about 200,000.16. The composition of claim 15 wherein the total amount of allparticulate material in the composition, by weight % of the composition,is about 10% or less.
 17. The composition of claim 15 wherein the totalamount of all particulate material in the composition, by weight % ofthe composition, is about 5% or less.
 18. The composition of claim 15wherein the total amount of all particulate material in the composition,by weight % of the composition, is about 3% or less.
 19. The compositionof claim 15 wherein the particulate material consists essentially ofTiO₂.
 20. The composition of claim 15 wherein the apparent viscosity isfrom about 20,000 to about 150,000 centipoise.
 21. The composition ofclaim 15 wherein the apparent viscosity is from about 25,000 to about100,000 centipoise.
 22. A method of regulating skin condition comprisingtopically applying the composition of claim
 1. 23. The method of claim22 wherein regulating skin condition comprises masking imperfections onthe skin surface.